Molecular engineering of cyanine dyes to design a panchromatic response in Co-sensitized dye-sensitized solar cells

DOE PAGES

Pepe, Giulio; Cole, Jacqueline M.; Waddell, Paul G.; ...

2016-04-05

Cyanines are optically tunable dyes with high molar extinction coefficients, suitable for applications in co-sensitized dye-sensitized solar cells (DSCs); yet, barely thus applied. This might be due to the lack of a rational molecular design strategy that efficiently exploits cyanine properties. This study computationally re-designs these dyes, to broaden their optical absorption spectrum and create dye···TiO 2 binding and co-sensitization functionality. This is achieved via a stepwise molecular engineering approach. Firstly, the structural and optical properties of four parent dyes are experimentally and computationally investigated: 3,3’-diethyloxacarbocyanine iodide, 3,3’-diethylthiacarbocyanine iodide, 3,3’-diethylthiadicarbocyanine iodide and 3,3’-diethylthiatricarbocyanine iodide. Secondly, the molecules are theoretically modifiedmore » and their energetics are analyzed and compared to the parent dyes. A dye···TiO 2 anchoring group (carboxylic or cyanoacrylic acid), absent from the parent dyes, is chemically substituted at different molecular positions to investigate changes in optical absorption. We find that cyanoacrylic acid substitution at the para-quinoidal position affects the absorption wavelength of all parent dyes, with an optimal bathochromic shift of ca. 40 nm. The theoretical lengthening of the polymethine chain is also shown to effect dye absorption. Two molecularly engineered dyes are proposed as promising co-sensitizers. Finally, corresponding dye···TiO 2 adsorption energy calculations corroborate their applicability, demonstrating the potential of cyanine dyes in DSC research.« less

Optical Properties of Nano-Spherical Gold Doped Dye Solution Hybrid

NASA Astrophysics Data System (ADS)

Hoa, D. Q.; Lien, N. T. H.; Ha, C. V.; Nhung, T. H.; Long, P.

2011-03-01

Gold nanoparticles with average diameter of 16 nm which are coated with Cetrimonium Bromide (CTAB) by chemical method are dissolved in dye solution at different concentrations. The absorption spectra of the dye mixture appeared almost unchanged at low concentrations of gold nanoparticles (around 1×1014 cm-3) despite its fluorescence intensity increased many-fold. Energy transfer from gold nanoparticles to dye molecules occurs through surface plasmon resonance(SPR). The fluorescence of rhodamine 610 (Rh610) dye molecules co-adsorbed within 16 nm gold nanoparticles assemblies can be useful for enhancing gain in lasing emission. An increase in laser efficiency by a factor of one and half times stronger compared to the single Rh610 dye suggest the potential of using the mixture of rhodamine dye with gold nanoparticles as laser medium in the configuration of quenching distributed feedback dye laser.

Nonlinearities of polymethine and squarylium molecules for optical limiting

NASA Astrophysics Data System (ADS)

Lim, Jin Hong

Optical limiting, a process that reduces transmittance at high laser input energies (irradiance, fluence), is of interest in applications where sensitive optical components, e.g. detectors, are vulnerable to damage by the laser beam. Polymethine and squarylium dyes show strong reverse saturable absorption (RSA) at 532 nm. RSA is a process by which weak linear absorption populates excited states which subsequently absorb strongly. Thus, low inputs are transmitted while high inputs are absorbed. This nonlinear absorption is determined by the ground and excited-state absorption cross sections as well as excited state lifetimes of the molecular system. We characterized a series of polymethine and squarine molecules in ethanol and polyurethane acrylate polymeric host (PUA) using Z-scan and pump-probe techniques at the second harmonic of the Nd:YAG laser system. A comparison of the properties in these two hosts is made. Some of these dyes show a large ratio of excited to ground state absorption cross section, ~200, which is larger than any previously reported values. In order to determine the wavelength dependence of the nonlinearities of these molecules, we also performed Z-scan and pump-probe experiments at wavelengths from 440 to 650 nm using a picosecond optical parametric oscillator (OPO) which is synchronously pumped by the third-harmonic of a modelocked train of Nd:YAG laser pulses. The OPO is continuously tunable from 400 to 700 nm using two critically phase-matched BBO crystals mounted for walkoff compensation. A polymethine dye in PUA (PD #3), which is one of the best polymethine dyes at 532 nm, shows strong RSA over a broad spectral range from 480 to 620 nm. while a squarylium dye shows RSA over a relatively narrow spectral range from 500 to 560 nm. However, the excited state lifetimes (~2.5 ns in PUA) are shorter than desirable for good nanosecond optical limiting (10 ns) and at high inputs (>=0.36 J/cm2) the limiting properties are reduced. Extensive measurements of these molecules along with computer modeling indicate that the reduced limiting at high inputs is due to molecular degradation induced after a trans-cis conformational change. Evidence for this and possible methods to eliminate this problem are presented.

An organic dye-polymer (phenol red-poly (vinyl alcohol)) composite architecture towards tunable -optical and -saturable absorption characteristics

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

Sreedhar, Sreeja, E-mail: sreejasreedhar83@gmail.com; Muneera, C. I., E-mail: drcimuneera@hotmail.com; Illyaskutty, Navas

2016-05-21

Herein, we demonstrate that blending an organic dye (guest/filler), with a vinyl polymer (host template), is an inexpensive and simple approach for the fabrication of multifunctional photonic materials which could display an enhancement in the desirable properties of the constituent materials and, at the same time provide novel synergistic properties for the guest-host system. A new guest-host nanocomposite system comprising Phenol Red dye and poly (vinyl alcohol) as guest and host template, respectively, which exhibits tunable optical characteristics and saturable absorption behavior, is introduced. The dependence of local electronic environment provided by the polymer template and the interactions of themore » polymer molecules with the encapsulated guest molecules on the observed optical/nonlinear absorption behavior is discussed. An understanding of the tunability of the optical/ photophysical processes, with respect to the filler content, as discussed herein could help in the design of improved optical materials for several photonic device applications like organic light emitting diodes and saturable absorbers.« less

First Principles Optical Absorption Spectra of Organic Molecules Adsorbed on Titania Nanoparticles

NASA Astrophysics Data System (ADS)

Baishya, Kopinjol; Ogut, Serdar; Mete, Ersen; Gulseren, Oguz; Ellialtioglu, Sinasi

2012-02-01

We present results from first principles computations on passivated rutile TiO2 nanoparticles in both free-standing and dye-sensitized configurations to investigate the size dependence of their optical absorption spectra. The computations are performed using time-dependent density functional theory (TDDFT) as well as GW-Bethe-Salpeter-Equation (GWBSE) methods and compared with each other. We interpret the first principles spectra for free-standing TiO2 nanoparticles within the framework of the classical Mie-Gans theory using the bulk dielectric function of TiO2. We investigate the effects of the titania support on the absorption spectra of a particular set of perylene-diimide (PDI) derived dye molecules, namely brominated PDI (Br2C24H8N2O4) and its glycine and aspartine derivatives.

Adsorption of methyl green on montmorillonite

NASA Astrophysics Data System (ADS)

Margulies, Leon; Rozen, Harel

1986-03-01

Adsorption of the dye methyl green (MG) on Na -montmorillonite (Clay) takes place through a cation exchange mechanism. At low and high MG loads, each MG molecule replaces approximately two and one Na + ions, respectively. Interactions between MG and Clay were studied using visible absorption and FTIR spectroscopies, and the orientation of the adsorbed molecules were determined by infrared linear dichroism and X-ray powder diffraction. The dye molecules are preferentially oriented with their plane parallel to the clay surface. The influence of MG load on the adsorption of two additional organic molecules, benzyl benzoate and benzophenone, was also studied.

Design of butterfly type organic dye sensitizers with double electron donors: The first principle study

NASA Astrophysics Data System (ADS)

Yang, Zhenqing; Shao, Di; Li, Juan; Tang, Lian; Shao, Changjin

2018-05-01

In this work, we designed a series of butterfly type organic dyes, named ME07-ME13 by introducing such as triphenylamine, phenothiazine, coumarin groups etc. as electron donors and further investigated their absorption spectra using density functional theory (DFT) and time-dependent DFT (TDDFT). All designed dyes cover the entire visible absorption spectrum from 300 to 800 nm. It's fascinating that ME13 molecule has two absorption peak and the molar coefficient of two absorption peaks are above 4.645 × 104 M-1·cm-1. The light absorption area of ME13 exhibits an increment of 16.5-19.1% compared to ME07-ME12. Furthermore, we performed a detailed analysis on their geometrical and electronic properties, including molecular structures, energy levels, light harvesting efficiency (LHE), driving force (ΔGinject), regeneration (ΔGregen),electron dipole moments (μnormal), intermolecular electron transfer and dye/(TiO2)38 system electron transitions. The results of calculation reveal that double coumarin donors in ME13 are promising functional groups for butterfly type organic dye sensitizers. It is expected that the design of double donors can provide a new strategy and guidance for the investigation in high efficiency dye-sensitized devices.

Spectroscopic manifestations of hybrid association of CdS colloidal quantum dots with J-aggregates of a thiatrimethine cyanine dye

NASA Astrophysics Data System (ADS)

Ovchinnikov, O. V.; Smirnov, M. S.; Shapiro, B. I.; Dedikova, A. O.; Shatskikh, T. S.

2015-11-01

We have found spectroscopic manifestations of hybrid association in mixtures of CdS colloidal quantum dots with an average size of 2.5-4.2 nm with J-aggregates of pyridinium salt of the 3,3'-di-(γ- sulfopropyl)-9-ethyl-4,5,4',5'-dibenzo-thiacarbocyanine betaine dye that were prepared by the sol-gel method in gelatin. Observed changes of the spectral properties of J-aggregates of dye molecules due to their hybrid association with CdS quantum dots are ensured by steric transformations of dye molecules, which lead to the formation of luminescent trans-J-aggregates. The hybrid association is accompanied by the quenching of the recombination luminescence band of CdS quantum dots (540-640 nm) and by an increase in the luminescence intensity of J-aggregates of dye molecules (670-680 nm). This regularity becomes enhanced with an increase in the ratio of the number of dye molecules to the number of quantum dots [ n dye]: [ n QD] and in the degree of overlap between the luminescence spectrum of quantum dots and the absorption spectrum of J-aggregates, which indicates that there is a resonant nonradiative transfer of the electronic excitation energy from recombination luminescence centers in CdS quantum dots to trans-J-aggregates of dye molecules conjugated to them.

Spin-coated Films of Squarylium Dye J-Aggregates Exhibiting Ultrafast Optical Responses

NASA Astrophysics Data System (ADS)

Tatsuura, Satoshi; Tian, Minquan; Furuki, Makoto; Sato, Yasuhiro; Pu, Lyong Sun; Wada, Osamu

2000-08-01

The formation of J-aggregates of squarylium dye derivatives in spin-coated films is reported. Squarylium dye derivatives with dipropylamino bases are found to spontaneously aggregate in a spin-coated film. Aggregation is promoted when dye molecules are dispersed in a poly(vinyl alcohol) film, and when a spin-coated film of dye molecules is heated in the presence of acid vapor. In particular, J-aggregates formed by exposure to acetic acid vapor show the narrowest spectral width. J-aggregates formed by the acid treatment method are stable at room temperature and the spectral full-width at half maximum of the J-band is 20 nm. Optical response of the acid-treated film is confirmed to exhibit a short relaxation time of bleached absorption of 300 fs.

Effect of auxiliary group for p-type organic dyes in NiO-based dye-sensitized solar cells: The first principal study

NASA Astrophysics Data System (ADS)

Li, Juan; Zhang, Shijie; Shao, Di; Yang, Zhenqing; Zhang, Wansong

2018-03-01

Auxiliary acceptor groups play a crucial role in D-A-π-A structured organic dyes. In this paper, we designed three D-A-π-A structured organic molecules based on the prototype dye QT-1, named ME18-ME20, and further investigated their electronic and optical properties with density functional theory (DFT) and time-dependent DFT (TDDFT). The calculated results indicate that the scope and intensity of dyes' absorption spectra have some outstanding changes by inserting auxiliary groups. ME20 has not only 152 nm redshifts to long wave orientation, but also 78% increased oscillator strength compared to QT-1, and its absorption spectrum broadens region even up to 1400 nm. Then, we studied the reason that the effect of the introduced different auxiliary acceptor groups in these dyes through their ground states geometries and energy levels, electron transfer and recombination rate.

Effect of TiO2 nanoparticles on some photophysical characteristics of ketocyanine dyes.

PubMed

Thipperudrappa, Javuku; Raghavendra, U P; Basanagouda, Mahantesha

2017-11-01

The effect of titanium dioxide (TiO 2 ) nanoparticles (NPs) on photophysical characteristics of 2,5-di[(E)-1-(4-dimethylaminophenyl) methylidine]-1-cyclopentanone (2,5-DMAPMC) and 2,5-di[(E)-1-(4-diethylaminophenyl)methylidine]-1-cyclopentanone (2,5-DEAPMC) ketocyanine dyes has been studied using absorption, steady-state and time-resolved fluorescence spectroscopy. The magnitudes of association constants determined based on modified absorption spectrum of dyes due to the presence of TiO 2 NPs indicate the interaction of TiO 2 NPs with dye molecules. The quenching of fluorescence intensity of dyes by TiO 2 NPs is observed and it follows linear Stern-Volmer (S-V) equation. The magnitude of quenching rate parameter suggests the involvement of static quenching mechanism. The involvement of electron transfer process in reducing fluorescence intensity of dyes has been discussed. Also, varying influence of TiO 2 NPs on two dyes is explained based on the presence of different alkyl substituent in two dyes. Copyright © 2017 John Wiley & Sons, Ltd.

Polymethine and squarylium molecules with large excited-state absorption

NASA Astrophysics Data System (ADS)

Lim, Jin Hong; Przhonska, Olga V.; Khodja, Salah; Yang, Sidney; Ross, T. S.; Hagan, David J.; Van Stryland, Eric W.; Bondar, Mikhail V.; Slominsky, Yuriy L.

1999-07-01

We study nonlinear absorption in a series of ten polymethine dyes and two squarylium dyes using Z-scan, pump-probe and optical limiting experiments. Both picosecond and nanosecond characterization were performed at 532 nm, while picosecond measurements were performed using an optical parametric oscillator (OPO) from 440 to 650 nm. The photophysical parameters of these dyes including cross sections and excited-state lifetimes are presented both in solution in ethanol and in an elastopolymeric material, polyurethane acrylate (PUA). We determine that the dominant nonlinearity in all these dyes is large excited-state absorption (ESA), i.e. reverse saturable absorption. For several of the dyes we measure a relatively large ground-state absorption cross section, σ01, which effectively populates an excited state that possesses an extremely large ESA cross section, σ12. The ratios of σ12/ σ01 are the largest we know of, up to 200 at 532 nm, and lead to very low thresholds for optical limiting. However, the lifetimes of the excited state are of the order of 1 ns in ethanol, which is increased to up to 3 ns in PUA. This lifetime is less than optimum for sensor protection applications for Q-switched inputs, and intersystem crossing times for these molecules are extremely long, so that triplet states are not populated. These parameters show a significant improvement over those of the first set of this class of dyes studied and indicate that further improvement of the photophysical parameters may be possible. From these measurements, correlations between molecular structure and nonlinear properties are made. We propose a five-level, all-singlet state model, which includes reorientation processes in the first excited state. This includes a trans- cis conformational change that leads to the formation of a new state with a new molecular configuration which is also absorbing but can undergo a light-induced degradation at high inputs.

Interactions of Fluorescein Dye with Spherical and Star Shaped Gold Nanoparticles.

PubMed

Pal, Gopa Dutta; Paul, Somnath; Bardhan, Munmun; Ganguly, Tapan

2018-04-01

UV-vis absorption, FT-IR, steady state fluorescence and fluorescence lifetime measurements were made on Fluorescein dye (Fl dye) molecules in presence of gold nanoparticles of different morphologies: spherical gold nanoparticles (GNP) and star shaped gold nanoparticles (GNS). The experimental observations demonstrate that Fl dye molecules form dimers when adsorbed on nanosurface of spherical gold particles. On the other hand possibly due to lack of adsorption on the surface of GNS the dye molecules were unable to form dimers. The projected tips on the surface of GNS may possibly hinder the dyes to adsorb on the surface of this nanoparticle. From the spectral analysis and measurements of thermodynamic parameters it is inferred that two different types of ground state interactions occur between Fl-dye-GNP and Fl dye-GNS systems. Both the observed negative values of the thermodynamic parameters ΔH and ΔS in the case of the former system predict the possibility of occurrences of hydrogen bonding interactions between two neighboring Fl dye molecules when adsorbed on the nanosurface of GNP. On the other hand in Fl dye-GNS system electrostatic interactions appear to occur, as evidenced from negative ΔH and positive value of ΔS, between the positive charges residing on the tips of the nanoparticles and anionic form of Fl dye. It has been concluded that as the adsorption of organic dyes on solid surfaces is prerequisite for the degradation of dye pollutants, the present experimental observations demonstrate that GNP could be used as a better candidate than GNS in degradation mechanism of the xanthenes dyes.

Can H-aggregates serve as light-harvesting antennae? Triplet-triplet energy transfer between excited aggregates and monomer thionine in aerosol-OT solutions

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

Das, S.; Kamat, P.V.

1999-01-07

The cationic dye thionine undergoes slow dissolution in aerosol-OT (AOT) containing solutions of heptane and toluene. By controlling the ratio of [dye]/[AOT], it is possible to obtain varying amounts of monomer, dimer, and higher order aggregates (trimer) in dilute dye solutions. The thionine aggregates exhibit characteristic absorption maxima at 565 and 530 nm for the dimer and trimer forms, respectively. The singlet excited states of these dye aggregates are short-lived ({tau} = 40--63 ps) as they undergo efficient intersystem crossing to generate the triplet excited states. Triplet energy transfer from the excited dye aggregates to monomeric thionine molecules was observedmore » upon excitation with a 532 nm laser pulse. Pulse radiolysis experiments, in which the excited triplet states were generated indirectly, also confirm the finding that the triplet energy cascades down from excited trimer to dimer to monomeric dye. These studies demonstrate the possibility of using H-type dye aggregates as antenna molecules to harvest light energy whereby the aggregate molecules absorb light in different spectral regions and subsequently transfer energy to the monomeric dye.« less

Excited state characteristics of acridine dyes: acriflavine and acridine orange.

PubMed

Sharma, Vijay K; Sahare, P D; Rastogi, Ramesh C; Ghoshal, S K; Mohan, D

2003-06-01

The magnitude of the Stokes shift (frequency shifts in absorption and fluorescence spectra) is observed on changing the solvents and further has been used to calculate experimentally the dipole moments (ground state and excited state) of acriflavine and acridine orange dye molecules. Theoretically, dipole moments are calculated using PM 3 Model. The dipole moments of excited states, for both molecules investigated here, are higher than the corresponding values in the ground states. The increase in the dipole moment has been explained in terms of the nature of the excited state. Acriflavine dye overcomes the non-lasing behaviour of acridine orange due to quaternization of the central nitrogen atom.

Optical study of xanthene-type dyes in nano-confined liquid

NASA Astrophysics Data System (ADS)

Mahdi Shavakandi, Seyyed; Alizadeh, Khalil; Sharifi, Soheil; Marti, Othmar; Amirkhani, Masoud

2017-04-01

The optical activity of dye molecules in different environments is of great interest for many applications such as laser system or biological imaging. We investigate the fluorescence and absorption spectrum of nano-confined xanthene dyes (RhB and fluorescein sodium salt) in a two-phase liquid. Each show very distinct optical behavior in the water phase of a reverse microemulsion. Their optical properties such as absorption and fluorescence for different concentrations of dye and nanodroplets are investigated. We show that for the same concentration of dye in the microemulsion the peak of fluorescence intensity is varied by altering the concentration of nanodroplets. However, the trend of the change is widely different depending on the hydrophobicity of dyes. Quantum-mechanical second order perturbation theory is used to calculate the ratio of dipole moments in the ground and excited states, which accounts for the Stokes shift in fluorescence peak. Photon correlation spectroscopy is employed to check the trace of the dye in the oil phase of the microemulsion.

IV INTERNATIONAL CONFERENCE ON ATOM AND MOLECULAR PULSED LASERS (AMPL'99): Spectral properties of optical anisotropy induced by laser radiation in dye solutions

NASA Astrophysics Data System (ADS)

Pikulik, L. G.; Chernyavskii, V. A.; Grib, A. F.

2000-06-01

Spectral studies of induced quasi-crystal properties (which can be quantitatively characterised by the difference in the refractive indices of ordinary and extraordinary waves, Δn=no—ne) in Rhodamine 6G and Rhodamine 4C solutions in glycerine excited in the visible and UV ranges of the absorption spectrum are presented. It is demonstrated that the observed spectral dependences of Δn of these dye solutions excited in the visible (long-wavelength) and UV (short-wavelength) ranges of the absorption spectrum can be interpreted in terms of an oscillator model of a molecule. The proposed method for the analysis of induced optical anisotropy in solutions of organic compounds allows the relative orientation of oscillators in a molecule and, thus, the relative orientation of electronic transitions in a molecule to be determined in a reliable way.

The identification of hydrophobic sites on the surface of proteins using absorption difference spectroscopy of bromophenol blue.

PubMed

Bertsch, M; Mayburd, A L; Kassner, R J

2003-02-15

Hydrophobic sites on the surface of protein molecules are thought to have important functional roles. The identification of such sites can provide information about the function and mode of interaction with other cellular components. While the fluorescence enhancement of polarity-sensitive dyes has been useful in identifying hydrophobic sites on a number of targets, strong intrinsic quenching of Nile red and ANSA dye fluorescence is observed on binding to a cytochrome c('). Fluorescence quenching is also observed to take place in the presence of a variety of other biologically important molecules which can compromise the quantitative determination of binding constants. Absorption difference spectroscopy is shown not to be sensitive to the presence of fluorescence quenchers but sensitive enough to measure binding constants. The dye BPB is shown to bind to the same hydrophobic sites on proteins as polarity-sensitive fluorescence probes. The absorption spectrum of BPB is also observed to be polarity sensitive. A binding constant of 3x10(6)M(-1) for BPB to BSA has been measured by absorption difference spectroscopy. An empirical correlation is observed between the shape of the absorption difference spectrum of BPB and the polarity of the environment. The results indicate that absorption difference spectroscopy of BPB provides a valuable supplement to fluorescence for determining the presence of hydrophobic sites on the surface of proteins as well as a method for measuring binding constants.

Persistent optical hole-burning spectroscopy of nano-confined dye molecules in liquid at room temperature: Spectral narrowing due to a glassy state and extraordinary relaxation in a nano-cage

NASA Astrophysics Data System (ADS)

Murakami, Hiroshi

2018-04-01

Persistent optical hole-burning spectroscopy has been conducted for a dye molecule within a very small (˜1 nm) reverse micelle at room temperature. The spectra show a spectral narrowing due to site-selective excitation. This definitely demonstrates that the surroundings of the dye molecule are in a glassy state regardless of a solution at room temperature. On the other hand, the hole-burning spectra exhibit large shifts from excitation frequencies, and their positions are almost independent of excitation frequencies. The hole-burning spectra have been theoretically calculated by taking account of a vibronic absorption band of the dye molecule under the assumption that the surroundings of the dye molecule are in a glassy state. The calculated results agree with the experimental ones that were obtained for the dye molecule in a polymer glass for comparison, where it has been found that the ratio of hole-burning efficiencies of vibronic- to electronic-band excitations is quite high. On the other hand, the theoretical results do not explain the large spectral shift from the excitation frequency and small spectral narrowing observed in the hole-burning spectra measured for the dye-containing reverse micelle. It is thought that the spectral shift and broadening occur within the measurement time owing to the relaxation process of the surroundings that are hot with the thermal energy deposited by the dye molecule optically excited. Furthermore, the relaxation should be temporary because the cooling of the inside of the reverse micelle takes place with the dissipation of the excess thermal energy to the outer oil solvent, and so the surroundings of the dye molecule return to the glassy state and do not attain the thermal equilibrium. These results suggest that a very small reverse micelle provides a unique reaction field in which the diffusional motion can be controlled by light in a glassy state.

Photophysical studies on the interaction of acridinedione dyes with universal protein denaturant: guanidine hydrochloride.

PubMed

Kumaran, R; Varalakshmi, T; Malar, E J Padma; Ramamurthy, P

2010-09-01

Photophysical studies of photoinduced electron transfer (PET) and non-PET based acridinedione dyes with guanidine hydrochloride (GuHCl) were carried out in water and methanol. Addition of GuHCl to photoinduced electron transfer (PET) based acridinedione dye (ADR 1) results in a fluorescence enhancement, whereas a non-PET based dye (ADR 2) shows no significant change in the fluorescence intensity and lifetime. Addition of GuHCl to ADR 1 dye in methanol results in single exponential decay behaviour, on the contrary a biexponential decay pattern was observed on the addition of GuHCl in water. Absorption and emission spectral studies of ADR 1 dye interaction with GuHCl reveals that the dye molecule is not in the protonated form in aqueous GuHCl solution, and the dye is confined to two distinguishable microenvironment in the aqueous phase. A large variation in the microenvironment around the dye molecule is created on the addition of GuHCl and this was ascertained by time-resolved area normalized emission spectroscopy (TRANES) and time-resolved emission spectroscopy (TRES). The dye molecule prefers to reside in the hydrophobic microenvironment, rather in the hydrophilic aqueous phase is well emphasized by time-resolved fluorescence lifetime studies. The mechanism of fluorescence enhancement of ADR 1 dye by GuHCl is attributed to the suppression of the PET process occurring through space.

Indium-chlorine and gallium-chlorine tetrasubstituted phthalocyanines in a bulk system, Langmuir monolayers and Langmuir-Blodgett nanolayers--spectroscopic investigations.

PubMed

Bursa, B; Wróbel, D; Biadasz, A; Kędzierski, K; Lewandowska, K; Graja, A; Szybowicz, M; Durmuş, M

2014-07-15

The paper deals with spectroscopic characterization of metallic phthalocyanines (Pc's) (indium and gallium) complexed with chlorine and substituted with four benzyloxyphenoxy peripheral groups in bulk systems, 2D Langmuir monolayers and Langmuir-Blodgett nanolayers. An influence of the molecular structure of dyes (the presence of metal and of substitutes attached to the phthalocyanine macroring) on the in situ measurements of light absorption is reported. Molecular arrangement of the phthalocyanine molecular skeleton in the Langmuir monolayers on water substrate and in the Langmuir-Blodgett nanolayers is evaluated. A comparison of the light absorption spectra of the phthalocyanine monolayers with the spectra of the dyes in solution supports the existence of dye aggregates in the monolayer. It was shown that the type of dye aggregates (oblique and H types) depends markedly on the dye molecular structures. The NIR-IR, IR reflection-absorption and Raman spectra are also monitored for Langmuir-Blodgett nanolayers in non-polarized and polarized light. It was shown that the dye molecules in the Langmuir-Blodgett layers are oriented nearly vertically with respect to a gold substrate. Copyright © 2014 Elsevier B.V. All rights reserved.

Effects of dyes, gold nanocrystals, pH, and metal ions on plasmonic and molecular resonance coupling.

PubMed

Ni, Weihai; Chen, Huanjun; Su, Jing; Sun, Zhenhua; Wang, Jianfang; Wu, Hongkai

2010-04-07

The effects of various factors on the resonance coupling between elongated Au nanocrystals and organic dyes have been systematically investigated through the preparation of hybrid nanostructures between Au nanocrystals and the electrostatically adsorbed dye molecules. A nanocrystal sample is chosen for each dye to match the longitudinal plasmon resonance wavelength with the absorption peak wavelength of the dye as close as possible so that the resonance coupling strength can be maximized. The resonance coupling strength is found to approximately increase as the molecular volume-normalized absorptivity is increased. It is mainly determined by the plasmon resonance energy of the Au nanocrystals instead of their shapes and sizes. Moreover, the resonance coupling can be reversibly controlled if the dye in the hybrid nanostructures is pH-sensitive. The coupling can also be weakened in the presence of metal ions. These results will be highly useful for designing resonance coupling-based sensing devices and for plasmon-enhanced spectroscopy.

Device and method for luminescence enhancement by resonant energy transfer from an absorptive thin film

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

Akselrod, Gleb M.; Bawendi, Moungi G.; Bulovic, Vladimir

Disclosed are a device and a method for the design and fabrication of the device for enhancing the brightness of luminescent molecules, nanostructures, and thin films. The device includes a mirror, a dielectric medium or spacer, an absorptive layer, and a luminescent layer. The absorptive layer is a continuous thin film of a strongly absorbing organic or inorganic material. The luminescent layer may be a continuous luminescent thin film or an arrangement of isolated luminescent species, e.g., organic or metal-organic dye molecules, semiconductor quantum dots, or other semiconductor nanostructures, supported on top of the absorptive layer.

Multilayer Dye Aggregation at Dye/TiO2 Interface via π…π Stacking and Hydrogen Bond and Its Impact on Solar Cell Performance: A DFT Analysis.

PubMed

Zhang, Lei; Liu, Xiaogang; Rao, Weifeng; Li, Jingfa

2016-10-21

Multilayer dye aggregation at the dye/TiO 2 interface of dye-sensitized solar cells is probed via first principles calculations, using p-methyl red azo dye as an example. Our calculations suggest that the multilayer dye aggregates at the TiO 2 surface can be stabilized by π…π stacking and hydrogen bond interactions. Compared with previous two-dimensional monolayer dye/TiO 2 model, the multilayer dye aggregation model proposed in this study constructs a three-dimensional multilayer dye/TiO 2 interfacial structure, and provides a better agreement between experimental and computational results in dye coverage and dye adsorption energy. In particular, a dimer forms by π…π stacking interactions between two neighboring azo molecules, while one of them chemisorbs on the TiO 2 surface; a trimer may form by introducing one additional azo molecule on the dimer through a hydrogen bond between two carboxylic acid groups. Different forms of multilayer dye aggregates, either stabilized by π…π stacking or hydrogen bond, exhibit varied optical absorption spectra and electronic properties. Such variations could have a critical impact on the performance of dye sensitized solar cells.

Multilayer Dye Aggregation at Dye/TiO2 Interface via π…π Stacking and Hydrogen Bond and Its Impact on Solar Cell Performance: A DFT Analysis

PubMed Central

Zhang, Lei; Liu, Xiaogang; Rao, Weifeng; Li, Jingfa

2016-01-01

Multilayer dye aggregation at the dye/TiO2 interface of dye-sensitized solar cells is probed via first principles calculations, using p-methyl red azo dye as an example. Our calculations suggest that the multilayer dye aggregates at the TiO2 surface can be stabilized by π…π stacking and hydrogen bond interactions. Compared with previous two-dimensional monolayer dye/TiO2 model, the multilayer dye aggregation model proposed in this study constructs a three-dimensional multilayer dye/TiO2 interfacial structure, and provides a better agreement between experimental and computational results in dye coverage and dye adsorption energy. In particular, a dimer forms by π…π stacking interactions between two neighboring azo molecules, while one of them chemisorbs on the TiO2 surface; a trimer may form by introducing one additional azo molecule on the dimer through a hydrogen bond between two carboxylic acid groups. Different forms of multilayer dye aggregates, either stabilized by π…π stacking or hydrogen bond, exhibit varied optical absorption spectra and electronic properties. Such variations could have a critical impact on the performance of dye sensitized solar cells. PMID:27767196

Photon Antibunching in the Fluorescence of a Single Dye Molecule Trapped in a Solid

DTIC Science & Technology

1992-06-08

number) FIELD GROUP SUB-GROUP single-molecule spectroscopy in solids, photon antibunching, quantum-optics, nonclassical effects pentacene in p-terphenyl...emitted by an optically pumped single molecule of pentacene In a p-terphenyl host has been Investigated at short times. The correlation function...excitation tcclnique, certain individual pentacene impurity molecules in a p-terphenyl crystal 11 were observed to spectrally diffuse, i.e. their absorption

Picosecond absorption anisotropy of polymethine and squarylium dyes in liquid and polymeric media

NASA Astrophysics Data System (ADS)

Przhonska, Olga V.; Hagan, David J.; Novikov, Evgueni; Lepkowicz, Richard; Van Stryland, Eric W.; Bondar, Mikhail V.; Slominsky, Yuriy L.; Kachkovski, Alexei D.

2001-11-01

Time-resolved excitation-probe polarization measurements are performed for polymethine and squarylium dyes in ethanol and an elastopolymer of polyurethane acrylate (PUA). These molecules exhibit strong excited-state absorption in the visible, which results in reverse saturable absorption (RSA). In pump-probe experiments, we observe a strong angular dependence of the RSA decay kinetics upon variation of the angle between pump and probe polarizations. The difference in absorption anisotropy kinetics in ethanol and PUA is detected and analyzed. Anisotropy decay curves in ethanol follow a single exponential decay leading to complete depolarization of the excited state. We also observe complete depolarization in PUA, in which case the anisotropy decay follows a double exponential behavior. Possible rotations in the PUA polymeric matrix are connected with the existence of local microcavities of free volume. We believe that the fast decay component is connected with the rotation of molecular fragments and the slower decay component is connected with the rotation of entire molecules in local microcavities, which is possible because of the elasticity of the polymeric material.

Monomolecular layer of squarylium dye J aggregates exhibiting a femtosecond optical response of delocalized excitons

NASA Astrophysics Data System (ADS)

Furuki, Makoto; Pu, Lyong Sun; Sasaki, Fumio; Kobayashi, Shyunsuke; Tani, Toshiro

1998-05-01

We report on the demonstration of the femtosecond nonlinear optical response from a two-dimensional monomolecular layer of squarylium dye J aggregate at 5 °C. The formation of a monomolecular layer Langmuir film was achieved by spreading squarylium dye modified by two propyl and two hexyl groups at the air-water interface, which resulted in a very strong J band (o.d.=0.3) at 777 nm. The transient absorption spectra in a resonant pump-probe measurement showed a low absorption saturation power (9.7×106W/cm2) and an ultrafast response (300 fs), which are indicative of exciton delocalization over 18 molecules in this J aggregate, even at 5 °C.

Small molecule BODIPY dyes as non-fullerene acceptors in bulk heterojunction organic photovoltaics.

PubMed

Poe, Ambata M; Della Pelle, Andrea M; Subrahmanyam, Ayyagari V; White, William; Wantz, Guillaume; Thayumanavan, S

2014-03-18

A series of acceptor-donor-acceptor molecules containing terminal BODIPY moieties conjugated through the meso position were synthesized. Deep LUMO energy levels and good visible absorption led to their use as acceptors in bulk heterojunction solar cells. Inverted devices were fabricated, reaching efficiencies as high as 1.51%.

A comparative computational study of Csbnd N and Csbnd C bonding visible to NIR absorbing croconines

NASA Astrophysics Data System (ADS)

Chetti, Prabhakar; Tripathi, Anuj

2018-03-01

The lowest electronic excitations and charge transfer properties in two series of croconine dyes; 1) molecules with Csbnd N bonding, having an absorption in the visible region (400-600 nm) and 2) molecules with Csbnd C bonding, showing absorption in visible to near infrared (NIR) region (600-1100 nm) are analyzed by quantum-chemical calculations. The absorption maxima in Csbnd C bonding croconines (CCR) are always having 200-300 nm red shifted than its corresponding Csbnd N bonding croconines (NCR). The reason for this drastic red shift in CCR series than its corresponding NCR has been systematically studied by DFT, TDDFT and SAC-CI methods. It is found that, CCR series are with less charge transfer in nature and are having larger diradical character, whereas NCR series molecules showing larger charge transfer with lower diradical character. The change in bonding mode of central five membered croconate ring, from Csbnd N to Csbnd C, destabilization and/stabilization of HOMO LUMO levels were observed. This study may helpful in the design and synthesis of new visible to NIR absorbing croconine dyes which are useful in materials applications.

Thiazole yellow G dyed PVA films for optoelectronics: microstructrural, thermal and photophysical studies

NASA Astrophysics Data System (ADS)

Hebbar, Vidyashree; Bhajantri, R. F.; Naik, Jagadish; Rathod, Sunil G.

2016-07-01

In this paper, we report the microstructural, optical and fluorescence properties of poly(vinyl alcohol) (PVA)/Thiazole Yellow G (TY) dye composite prepared by solvent casting. The formation of change-transfer complex as a result of the interaction between the dye molecules and polymer chain is confirmed in FTIR, FT-Raman, XRD and DSC studies. SEM studies present the morphology of the samples. The UV-visible absorption spectra possess characteristic peaks of the TY dye corresponding to n-π* transition along with a characteristic peak of PVA. The composites exhibit the decreasing energy gap and increasing refractive index with an increase in wt.% of the TY dye. The fluorescence-quenching phenomena are observed in emission wavelength range of 391-406 nm upon excitation in the vicinity of absorption maxima (335 nm) with the quantum yield of 0.72 for lowest concentration of dye. The prepared composites bear high brightness, and improved thermal stability, which make them a promising material for sensors and optoelectronic applications.

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.

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

Triphenylamine based organic dyes for dye sensitized solar cells: A theoretical approach

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

Mohankumar, V.; Pandian, Muthu Senthil; Ramasamy, P., E-mail: ramasamyp@ssn.edu.in

2016-05-23

The geometry, electronic structure and absorption spectra for newly designed triphenylamine based organic dyes were investigated by density functional theory (DFT) and time dependent density functional theory (TD-DFT) with the Becke 3-Parameter-Lee-Yang-parr(B3LYP) functional, where the 6-31G(d,p) basis set was employed. All calculations were performed using the Gaussian 09 software package. The calculated HOMO and LUMO energies show that charge transfer occurs in the molecule. Ultraviolet–visible (UV–vis) spectrum was simulated by TD-DFT in gas phase. The calculation shows that all of the dyes can potentially be good sensitizers for DSSC. The LUMOs are just above the conduction band of TiO{sub 2}more » and their HOMOs are under the reduction potential energy of the electrolytes (I{sup −}/I{sub 3}{sup −}) which can facilitate electron transfer from the excited dye to TiO{sub 2} and charge regeneration process after photo oxidation respectively. The simulated absorption spectrum of dyes match with solar spectrum. Frontier molecular orbital results show that among all the three dyes, the “dye 3” can be used as potential sensitizer for DSSC.« less

Electronic structure of Fe- vs. Ru-based dye molecules

NASA Astrophysics Data System (ADS)

Johnson, Phillip S.; Cook, Peter L.; Zegkinoglou, Ioannis; García-Lastra, J. M.; Rubio, Angel; Ruther, Rose E.; Hamers, Robert J.; Himpsel, F. J.

2013-01-01

In order to explore whether Ru can be replaced by inexpensive Fe in dye molecules for solar cells, the differences in the electronic structure of Fe- and Ru-based dyes are investigated by X-ray absorption spectroscopy and first-principles calculations. Molecules with the metal in a sixfold, octahedral N cage, such as tris(bipyridines) and tris(phenanthrolines), exhibit a systematic downward shift of the N 1s-to-π* transition when Ru is replaced by Fe. This shift is explained by an extra transfer of negative charge from the metal to the N ligands in the case of Fe, which reduces the binding energy of the N 1s core level. The C 1s-to-π* transitions show the opposite trend, with an increase in the transition energy when replacing Ru by Fe. Molecules with the metal in a fourfold, planar N cage (porphyrins) exhibit a more complex behavior due to a subtle competition between the crystal field, axial ligands, and the 2+ vs. 3+ oxidation states.

Dye sensitized solar cell (DSSC) with natural dyes extracted from Jatropha leaves and purple Chrysanthemum flowers as sensitizer

NASA Astrophysics Data System (ADS)

Tahir, Dahlang; Satriani, Wilda; Gareso, P. L.; Abdullah, B.

2018-03-01

DSSC (Dye-Sensitized Solar Cell) prototype has been investigated using Jatropha leaves and purple Chrysanthemum flowers as natural dyes. DSSC consists of working electrode and counter electrode. A working electrode composed of semiconductor nanoparticles TiO2 that has been coated with dye molecules. Dye molecules serve as light photon catchers, while semiconductor nanoparticles TiO2 function to absorb and forward photons into electrons. In the electrode counter given catalyst carbon, serves to accelerate the reaction kinetics of triiodide reduction process on transparent conductive oxide (TCO). DSSC using TiO2 as a semiconductor material and natural dyes as sensitizer from Jatropha leaves and purple Chrysanthemum flowers are successful produced. The physical properties of the working electrode have been determined by using XRD and the chemical properties of the TiO2 powder and dye powder using FTIR and dye solution using UV-Vis. The resulted fabrications are also examined its I-V characteristics. The best performance is generated by mixed dye 1.91 x 10-3 % compared than those DSSC for dye extracted from Jatropha leaves or purple Chrysanthemum. The characterization results show that the higher of the absorption wavelength of the DSSC efficiency is high.

Evidence for Interfacial Halogen Bonding.

PubMed

Swords, Wesley B; Simon, Sarah J C; Parlane, Fraser G L; Dean, Rebecca K; Kellett, Cameron W; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

2016-05-10

A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-Molecule Three-Color FRET with Both Negligible Spectral Overlap and Long Observation Time

PubMed Central

Hohng, Sungchul

2010-01-01

Full understanding of complex biological interactions frequently requires multi-color detection capability in doing single-molecule fluorescence resonance energy transfer (FRET) experiments. Existing single-molecule three-color FRET techniques, however, suffer from severe photobleaching of Alexa 488, or its alternative dyes, and have been limitedly used for kinetics studies. In this work, we developed a single-molecule three-color FRET technique based on the Cy3-Cy5-Cy7 dye trio, thus providing enhanced observation time and improved data quality. Because the absorption spectra of three fluorophores are well separated, real-time monitoring of three FRET efficiencies was possible by incorporating the alternating laser excitation (ALEX) technique both in confocal microscopy and in total-internal-reflection fluorescence (TIRF) microscopy. PMID:20808851

Variations in thermo-optical properties of neutral red dye with laser ablated gold nanoparticles

NASA Astrophysics Data System (ADS)

Prakash, Anitha; Pathrose, Bini P.; Mathew, S.; Nampoori, V. P. N.; Radhakrishnan, P.; Mujeeb, A.

2018-05-01

We have investigated the thermal and optical properties of neutral red dye incorporated with different weight percentage of gold nanoparticles prepared by laser ablation method. Optical absorption studies confirmed the production of spherical nanoparticles and also the interactions of the dye molecules with gold nanoparticles. The quenching of fluorescence and the reduction in the lifetime of gold incorporated samples were observed and was due to the non-radiative energy transfer between the dye molecules and gold nanoparticles. Dual beam thermal lens technique has been employed to measure the heat diffusion in neutral red with various weight percentage of gold nano sol dispersed in ethanol. The significant outcome of the experiment is that, the overall heat diffusion is slower in the presence of gold nano sol compared to that of dye alone sample. Brownian motion is suggested to be the main mechanism of heat transfer under the present conditions. The thermal diffusivity variations of samples with respect to different excitation power of laser were also studied.

Additive-induced aggregate changes of two structurally similar dyes in aqueous solutions: A comparative photophysical study.

PubMed

Ghanadzadeh Gilani, A; Poormohammadi-Ahandani, Z; Kian, R

2018-01-15

Absorption and emission spectral characteristics of the two structurally similar phenothiazine dyes, azure B and toluidine blue, in aqueous solutions of the two sets of molecular additives (ureas and monosaccharides) were studied as a function of the dye and additive concentrations. The absorption spectra of the dyes were also studied in pure tetramethylurea with an aprotic nature. The spectral data were analyzed using DECOM Program. The dimer structure of the interacting molecules in these dyes was discussed using the exciton model. The urea class of additives was found to act as water structure-breakers over the range of studied concentration. The carbohydrate additives were found to act as water structure-breakers at low concentrations. However, the water structure breaking process may be disfavored by the additive-additive interactions at higher concentrations. It can be concluded that at low additive concentrations, the main driving force for breaking the dye association is water-additive interaction, which disrupts the water hydrogen bonds induced by the additives. However, at the high additive concentrations, the different phenomena including additive-additive and additive-dye interactions can change the structure, strength, and aggregative properties of the dyes. Finally, the urea in water induces noticeably fluorescence quenching in emission spectra of both the dyes. Copyright © 2017 Elsevier B.V. All rights reserved.

Additive-induced aggregate changes of two structurally similar dyes in aqueous solutions: A comparative photophysical study

NASA Astrophysics Data System (ADS)

Ghanadzadeh Gilani, A.; Poormohammadi-Ahandani, Z.; Kian, R.

2018-01-01

Absorption and emission spectral characteristics of the two structurally similar phenothiazine dyes, azure B and toluidine blue, in aqueous solutions of the two sets of molecular additives (ureas and monosaccharides) were studied as a function of the dye and additive concentrations. The absorption spectra of the dyes were also studied in pure tetramethylurea with an aprotic nature. The spectral data were analyzed using DECOM Program. The dimer structure of the interacting molecules in these dyes was discussed using the exciton model. The urea class of additives was found to act as water structure-breakers over the range of studied concentration. The carbohydrate additives were found to act as water structure-breakers at low concentrations. However, the water structure breaking process may be disfavored by the additive-additive interactions at higher concentrations. It can be concluded that at low additive concentrations, the main driving force for breaking the dye association is water-additive interaction, which disrupts the water hydrogen bonds induced by the additives. However, at the high additive concentrations, the different phenomena including additive-additive and additive-dye interactions can change the structure, strength, and aggregative properties of the dyes. Finally, the urea in water induces noticeably fluorescence quenching in emission spectra of both the dyes.

Ultrafast photodynamics of the indoline dye D149 adsorbed to porous ZnO in dye-sensitized solar cells.

PubMed

Rohwer, Egmont; Richter, Christoph; Heming, Nadine; Strauch, Kerstin; Litwinski, Christian; Nyokong, Tebello; Schlettwein, Derck; Schwoerer, Heinrich

2013-01-14

We investigate the ultrafast dynamics of the photoinduced electron transfer between surface-adsorbed indoline D149 dye and porous ZnO as used in the working electrodes of dye-sensitized solar cells. Transient absorption spectroscopy was conducted on the dye in solution, on solid state samples and for the latter in contact to a I(-)/I(3)(-) redox electrolyte typical for dye-sensitized solar cells to elucidate the effect of each component in the observed dynamics. D149 in a solution of 1:1 acetonitrile and tert-butyl alcohol shows excited-state lifetimes of 300±50 ps. This signature is severely quenched when D149 is adsorbed to ZnO, with the fastest component of the decay trace measured at 150±20 fs due to the charge-transfer mechanism. Absorption bands of the oxidized dye molecule were investigated to determine regeneration times which are in excess of 1 ns. The addition of the redox electrolyte to the system results in faster regeneration times, of the order of 1 ns. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[1]Benzothieno[3,2-b]benzothiophene-Based Organic Dyes for Dye-Sensitized Solar Cells.

PubMed

Capodilupo, Agostina L; Fabiano, Eduardo; De Marco, Luisa; Ciccarella, Giuseppe; Gigli, Giuseppe; Martinelli, Carmela; Cardone, Antonio

2016-04-15

Three new metal-free organic dyes with the [1]benzothieno[3,2-b]benzothiophene (BTBT) π-bridge, having the structure donor-π-acceptor (D-π-A) and labeled as 19, 20 and 21, have been designed and synthesized for application in dye-sensitized solar cells (DSSC). Once the design of the π-acceptor block was fixed, containing the BTBT as the π-bridge and the cyanoacrylic group as the electron acceptor and anchoring unit, we selected three donor units with different electron-donor capacity, in order to assemble new chromophores with high molar extinction coefficients (ε), whose absorption features well reflect the good performance of the final DSSC devices. Starting with the 19 dye, which shows a molar extinction coefficient ε of over 14,000 M(-1) cm(-1) and takes into account the absorption maximun at the longer wavelength, the substitution of the BFT donor unit with the BFA yields a great enhancement of absorptivity (molar extinction coefficient ε > 42,000 M(-1) cm(-1)), until reaching the higher value (ε > 69,000 M(-1) cm(-1)) with the BFPhz donor unit. The good general photovoltaic performances obtained with the three dyes highlight the suitable properties of electron-transport of the BTBT as the π-bridge in organic chromophore for DSSC, making this very cheap and easy to synthesize molecule particularly attractive for efficient and low-cost photovoltaic devices.

Absorption spectrum analysis based on singular value decomposition for photoisomerization and photodegradation in organic dyes

NASA Astrophysics Data System (ADS)

Kawabe, Yutaka; Yoshikawa, Toshio; Chida, Toshifumi; Tada, Kazuhiro; Kawamoto, Masuki; Fujihara, Takashi; Sassa, Takafumi; Tsutsumi, Naoto

2015-10-01

In order to analyze the spectra of inseparable chemical mixtures, many mathematical methods have been developed to decompose them into the components relevant to species from series of spectral data obtained under different conditions. We formulated a method based on singular value decomposition (SVD) of linear algebra, and applied it to two example systems of organic dyes, being successful in reproducing absorption spectra assignable to cis/trans azocarbazole dyes from the spectral data after photoisomerization and to monomer/dimer of cyanine dyes from those during photodegaradation process. For the example of photoisomerization, polymer films containing the azocarbazole dyes were prepared, which have showed updatable holographic stereogram for real images with high performance. We made continuous monitoring of absorption spectrum after optical excitation and found that their spectral shapes varied slightly after the excitation and during recovery process, of which fact suggested the contribution from a generated photoisomer. Application of the method was successful to identify two spectral components due to trans and cis forms of azocarbazoles. Temporal evolution of their weight factors suggested important roles of long lifetimed cis states in azocarbazole derivatives. We also applied the method to the photodegradation of cyanine dyes doped in DNA-lipid complexes which have shown efficient and durable optical amplification and/or lasing under optical pumping. The same SVD method was successful in the extraction of two spectral components presumably due to monomer and H-type dimer. During the photodegradation process, absorption magnitude gradually decreased due to decomposition of molecules and their decaying rates strongly depended on the spectral components, suggesting that the long persistency of the dyes in DNA-complex related to weak tendency of aggregate formation.

Spectroscopic study of the interaction of styrylcyanine dyes Sbo, Sil and their derivatives with bovine serum albumin.

PubMed

Kurtaliev, Eldar N

2011-07-01

The spectral-luminescent characteristics of newly synthesized styrylcyanine dyes on the base of dyes Sbo ((E)-2-(4-(dimethylamino)styryl)-3-methylbenzo[d]oxazol-3-ium iodide) and Sil ((E)-2-(4-(dimethylamino)styryl)-1,3,3-trimethyl-3H-indolium perchlorate) in aqueous solutions without and in the presence of bovine serum albumin (BSA) were studied. It was established that the absorption spectra of dyes Tol-6, Dbo-10 and Dil-10 with increasing amount of BSA appear new bands with λ(max)=505 nm, λ(max)=512 nm and λ(max)=566 nm, respectively, whose intensity increases in proportion to the amount of albumin. The intensity of the glow of the main band of fluorescence in the presence of BSA sharply increases. The binding constant (K) and the number of binding sites (N) of studied dyes with BSA were determined. The dependence of binding constants with BSA on the dipole moment of dye molecules was determined, which indicates that besides electrostatic forces of attraction between molecules styrylcyanine dyes with BSA, hydrophobic interactions are essential. © Springer Science+Business Media, LLC 2011

Rationalizing the photophysical properties of BODIPY laser dyes via aromaticity and electron-donor-based structural perturbations

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

Waddell, Paul G.; Liu, Xiaogang; Zhao, Teng

2015-05-01

The absorption and fluorescence properties of six boron dipyrromethene (BODIPY) laser dyes with simple non-aromatic substituents are rationalized by relating them to observable structural perturbations within the molecules of the dyes. An empirical relationship involving the structure and the optical properties is derived using a combination of single-crystal X-ray diffraction data, quantum chemical calculations and electronic constants: i.e. the tendency of the pyrrole bond lengths towards aromaticity and the UV-vis absorption and fluorescence wavelengths correlating with the electron-donor properties of the substituents. The effect of molecular conformation on the solid-state optical properties of the dyes is also discussed. The findingsmore » in this study also demonstrate the usefulness and limitations of using crystal structure data to develop structure-property relationships in this class of optical materials, contributing to the growing effort to design optoelectronic materials with tunable properties via molecular engineering.« less

Light absorption and plasmon – exciton interaction in three-layer nanorods with a gold core and outer shell composed of molecular J- and H-aggregates of dyes

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

Shapiro, B I; Tyshkunova, E S; Kondorskiy, A D

2015-12-31

Optical properties of hybrid rod-like nanoparticles, consisting of a gold core, an intermediate passive organic layer (spacer) and outer layer of ordered molecular cyanine dye aggregates, are experimentally and theoretically investigated. It is shown that these dyes can form not only ordered J-aggregates but also H-aggregates (differing by the packing angle of dye molecules in an aggregate and having other spectral characteristics) in the outer shell of the hybrid nanostructure. Absorption spectra of synthesised three-layer nanorods are recorded, and their sizes are determined. The optical properties of the composite nanostructures under study are found to differ significantly, depending on themore » type of the molecular aggregate formed in the outer shell. The experimental data are quantitatively explained based on computer simulation using the finite-difference time-domain (FDTD) method, and characteristic features of the plasmon – exciton interaction in the systems under study are revealed. (nanophotonics)« less

Optical properties of voltage sensitive hemicyanine dyes of variable hydrophobicity confined within surfactant micelles

NASA Astrophysics Data System (ADS)

Naeem, Kashif; Naseem, Bushra; Shah, S. S.; Shah, Syed W. H.

2017-11-01

The optical properties of amphiphilic hemicyanine dyes with variable hydrophobicity, confined within anionic micelles of sodium dodecylbenzenesulfonate (NaDDBS) have been studied by UV-visible absorption spectroscopy. The confinement constant, K conf has been determined for each entrapped dye. The ion-pair formation between dye and surfactant causes a decline in electronic transition energy (ΔE T) when dye alkyl chains are smaller due to stabilization of both the ground and excited state. ΔE T values gradually increase with increase in dye hydrophobicity that hampers the electrostatic interaction with dialkylammonium moiety and consequently excited state stabilization is compromised. The average number of dye molecules trapped in a single micelle was also determined. The negative values of Gibbs free energy indicate that the dye entrapment within micelles is energetically favored. These findings have significance for developing functional materials with peculiar luminescent properties, especially for more effective probing of complex biological systems.

Mechanisms and chemistry of dye adsorption on manganese oxides-modified diatomite.

PubMed

Al-Ghouti, Mohammad A; Al-Degs, Yehya S; Khraisheh, Majeda A M; Ahmad, Mohammad N; Allen, Stephen J

2009-08-01

The investigations into structural changes which occur during adsorbent modification and the adsorption mechanisms are essential for an effective design of adsorption systems. Manganese oxides were impregnated onto diatomite to form the type known as delta-birnessite. Initial investigations established the effectiveness of manganese oxides-modified diatomite (MOMD) to remove basic and reactive dyes from aqueous solution. The adsorption capacity of MOMD for methylene blue (MB), hydrolysed reactive black (RB) and hydrolysed reactive yellow (RY) was 320, 419, and 204mg/g, respectively. Various analytical techniques were used to characterise the structure and the mechanisms of the dye adsorption process onto MOMD such as Fourier transform infrared (FTIR), X-ray diffraction (XRD) and atomic absorption spectrometry (A.A.). A small shift to higher values of the d-spacing of dye/MOMD was observed indicating that a small amount of the dye molecules were intercalated in the MOMD structure and other molecules were adsorbed on the external surface of MOMD. Two mechanisms of dye adsorption onto MOMD were proposed; intercalation of the dye in the octahedral layers and adsorption of the dye on the MOMD external surface. Moreover, the results demonstrated that the MOMD structure was changed upon insertion of MB and RY with an obvious decrease in the intensity of the second main peak of the MOMD X-ray pattern.

Spectrophotometric investigation of the hetero-association of Caffeine and thiazine dye in aqueous solution

NASA Astrophysics Data System (ADS)

Bolotin, P. A.; Baranovsky, S. F.; Evstigneev, M. P.

2006-06-01

The self-association of thiazine dye, Methylene Blue (MB), and its hetero-association with Caffeine (CAF), were studied in aqueous solution by means of spectrophotometry in the visible range of spectrum. Concentration and temperature dependences of molar absorption of the interacting molecules were used to analyse dynamic equilibrium in solution in terms of two-component model of molecular hetero-association. The magnitudes of equilibrium dimerization and hetero-association constants as well as thermodynamic parameters, enthalpy and entropy, were determined. The calculation of the fraction of different types of associates in the mixed solution, containing Methylene Blue and Caffeine, was done. It was concluded that the hetero-association of Methylene Blue and Caffeine molecules results in lower effective concentration of the dye in solution, which may account for the alteration of its biological activity.

Spectroscopic detection of halogen bonding resolves dye regeneration in the dye-sensitized solar cell.

PubMed

Parlane, Fraser G L; Mustoe, Chantal; Kellett, Cameron W; Simon, Sarah J; Swords, Wesley B; Meyer, Gerald J; Kennepohl, Pierre; Berlinguette, Curtis P

2017-11-24

The interactions between a surface-adsorbed dye and a soluble redox-active electrolyte species in the dye-sensitized solar cell has a significant impact on the rate of regeneration of photo-oxidized dye molecules and open-circuit voltage of the device. Dyes must therefore be designed to encourage these interfacial interactions, but experimentally resolving how such weak interactions affect electron transfer is challenging. Herein, we use X-ray absorption spectroscopy to confirm halogen bonding can exist at the dye-electrolyte interface. Using a known series of triphenylamine-based dyes bearing halogen substituents geometrically positioned for reaction with halides in solution, halogen bonding was detected only in cases where brominated and iodinated dyes were photo-oxidized. This result implies that weak intermolecular interactions between photo-oxidized dyes and the electrolyte can impact device photovoltages. This result was unexpected considering the low concentration of oxidized dyes (less than 1 in 100,000) under full solar illumination.

Concentration Dependence of Gold Nanoparticles for Fluorescence Enhancement

NASA Astrophysics Data System (ADS)

Solomon, Joel; Wittmershaus, Bruce

Noble metal nanoparticles possess a unique property known as surface plasmon resonance in which the conduction electrons oscillate due to incoming light, dramatically increasing their absorption and scattering of light. The oscillating electrons create a varying electric field that can affect nearby molecules. The fluorescence and photostability of fluorophores can be enhanced significantly when they are near plasmonic nanoparticles. This effect is called metal enhanced fluorescence (MEF). MEF from two fluorescence organic dyes, Lucifer Yellow CH and Riboflavin, was measured with different concentrations of 50-nm colloidal gold nanoparticles (Au-NP). The concentration range of Au-NP was varied from 2.5 to 250 pM. To maximize the interaction, the dyes were chosen so their emission spectra had considerable overlap with the absorption spectra of the Au-NP, which is common in MEF studies. If the dye molecules are too close to the surface of Au-NP, fluorescence quenching can occur instead of MEF. To try to observe this difference, silica-coated Au-NP were compared to citrate-based Au-NP; however, fluorescence quenching was observed with both Au-NP. This material is based upon work supported by the National Science Foundation under Grant Number NSF-ECCS-1306157.

Strong coupling between surface plasmon polariton and laser dye rhodamine 800

NASA Astrophysics Data System (ADS)

Valmorra, Federico; Bröll, Markus; Schwaiger, Stephan; Welzel, Nadine; Heitmann, Detlef; Mendach, Stefan

2011-08-01

We report on strong coupling between surface plasmon polaritons on a thin silver film and laser dye Rhodamine 800. Attenuated total reflection measurements reveal that the pure surface plasmon polaritons interact with the Rhodamine 800 absorption lines exhibiting pronounced anticrossings in the dispersion relation. We show that the corresponding energy gap can be tailored by the concentration of dye molecules in the dielectric matrix between 50 meV and 70 meV. We can well model our data by a classical transfer matrix approach as well as by a quantum mechanical coupled oscillator ansatz.

Two Photon Spectroscopy Can Serve as a Marker of Protein Denaturation Pathway.

PubMed

Das, Dipak Kumar; Islam, Sk Imadul; Samanta, Nirnay; Yadav, Yogendra; Goswami, Debabrata; Mitra, Rajib Kumar

2018-06-25

Rhodamine group of molecules are widely used dyes for imaging of biological molecules. Application of these dyes however includes a limitation that these molecules absorb in the visible range of the spectrum, which does not fall in the 'biologically transparent window' (BTW). Two photon absorption (TPA) process could come up with an alternate solution to this as these dyes could be excited in the near infrared (NIR) window to extract similar information. To validate this we have investigated TPA cross section (TPACS, σ 2 ) of two rhodamine dyes, namely Rhodamine 6G (R6G), Rhodamine B (RhB), site selectively bound with a model protein, bovine serum albumin (BSA), by exciting at 800 nm. Two photon spectroscopy and imaging confirms the binding of the dye to the protein. The decreases in TPACS with increasing temperature at a fixed BSA concentration excellently follows the temperature induced structural transition of BSA as the protein transforms from a molten globule to unfolded conformation beyond 60 °C, which has previously been established through circular dichroism (CD) measurements. The thus established resemblance in TPACS and CD measurement trends thus strongly affirms the suitability of TPA process in protein imaging and as an alternative marker to tracking its conformational transformations using NIR radiation.

Synthesis and characterization of Allium cepa L. as photosensitizer of dye-sensitized solar cell

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

Sutikno, E-mail: smadnasri@yahoo.com; Afrian, Noverdi; Supriadi,

The synthesis and characterization of Allium cepa L. used as natural pigment for natural dye sensitizer of solar cell has successfully done and anthocyanin is extracted. Anthocynin is color pigment of plant which has characteristic absorption spectrum of photon and excites electrons up to pigment molecules. As the anthocyanin absorbed light increases the excited electrons increase as well. The generated current also increases and it leads to the efficiency increase. The energy conversion efficiency of the cells sensitized with dye of Allium cepa L. was 3,045 x 10{sup −4}%. A simple technique was taken to fabricate dye sensitizer solar cellmore » is spincoating.« less

Novel water soluble NIR dyes: does charge matter?

NASA Astrophysics Data System (ADS)

Patonay, Gabor; Henary, Maged; Beckford, Garfield; Daube, Alison

2012-03-01

Near-Infrared (NIR) dyes are used as reporters, probes or markers in the biological and medical field. NIR dyes can be useful for investigating and characterizing biomolecular interactions or imaging which is possible because biological mammalian tissue has a low absorption window in the NIR region. Biomolecules such as proteins are known to bind to NIR dyes. Upon binding NIR dyes often exhibit spectral changes that can be used for characterizing the binding event. Serum albumins may be responsible for in vivo transport of NIR dyes. Studying this binding event can be useful when correlated to in vivo behavior of the NIR dye. The studies presented here use spectroscopic methods to investigate how NIR dyes that may be used in imaging, biological or bioanalytical applications bind to proteins, such as serum albumins. Our research group systematically synthesized several NIR dyes that have varying hydrophobicity, chromophore size and charge. During these investigations we developed novel NIR cyanine fluorophores having varying aqueous solubility and a variety of net charges. The binding properties of the carbocyanines change when charged or hydrophobic moieties are systematically varied. One of the properties we put a special emphasis on is what we call residual hydrophobicity of the NIR dye molecule which is defined as the unmasked (by the charged moieties) hydrophobicity of the molecule. Residual hydrophobicity may be responsible for binding the otherwise highly water soluble NIR dye to hydrophobic pockets of biomolecules. High residual hydrophobicity of a highly water soluble dye can be disadvantageous during biological, medical or similar applications.

Performance enhancement of dye-sensitized solar cells (DSSCs) using a natural sensitizer

NASA Astrophysics Data System (ADS)

Arifin, Zainal; Soeparman, Sudjito; Widhiyanuriyawan, Denny; Sutanto, Bayu; Suyitno

2017-01-01

Dye-sensitized solar cells (DSSCs) based on natural sensitizers have become a topic of significant research because of their urgency and importance in the energy conversion field and the following advantages: ease of fabrication, low-cost solar cell, and usage of nontoxic materials. The natural sensitizer in DSSCs is responsible for the absorption of light as well as the injection of charges to the conduction band of the semiconductor such as TiO2 nanoparticles. In this study, the chlorophyll extracted from papaya leaves was used as a natural sensitizer. Dye molecules were adsorbed by TiO2 nanoparticle surfaces when submerged in the dye solution for 24 h. The concentration of the dye solution influences both the amount of dye loading and the DSSC performance. The amount of adsorbed dye molecules by TiO2 nanoparticle was calculated using a desorption method. As the concentration of dye solution was increased, the dye loading capacity and power conversion efficiency increased. Above 90 mM dye solution concentration, however, the DSSC efficiency decreased because dye precipitated on the TiO2 nanostructure. These characteristics of DSSCs were analyzed under the irradiation of 100 mW/cm2. The best performance of DSSCs was obtained at 90 mM dye solution, with the values of Voc, Jsc, FF, and efficiency of DSSCs being 0.561 V, 0.402 mA/cm2, 41.65%, and 0.094%, respectively.

Influence of solvent and substituent on excited state characteristics of laser grade coumarin dyes.

PubMed

Sharma, Vijay K; Saharo, P D; Sharma, Neera; Rastogi, Ramesh C; Ghoshal, S K; Mohan, D

2003-04-01

Absorption and fluorescence emission of 4 and 7 substituted coumarins viz. C 440, C 490, C 485 and C 311 have been studied in various polar and non-polar organic solvents. These coumarin dyes are substituted with alkyl, amine and fluorine groups at 4- and 7-positions. They give different absorption and emission spectra in different solvents. The study leads to a possible assignment of energy level scheme for such coumarins including the effect on ground state and excited state dipole moments due to substitutions. Excited state dipole moments of these dyes are calculated by solvetochromic data experimentally and theoretically these are calculated by PM 3 method. The dipole moments in excited state, for all molecules investigated here, are higher than the corresponding values in the ground state. The increase in dipole moment has been explained in terms of the nature of excited state and resonance structure.

Theoretical description of efficiency enhancement in DSSCs sensitized by newly synthesized heteroleptic Ru complexes.

PubMed

Azar, Yavar T; Payami, Mahmoud

2015-11-28

Recently, some new series of heteroleptic ruthenium-based dyes, the so-called RD dyes, were designed and synthesized showing better performances compared to the well-known homoleptic N719. In this work, using the density-functional theory and its time-dependent extension, we have investigated the electronic structure and absorption spectra of these newly synthesized dyes, and compared the results to those of N3 dye to describe the variations of the properties due to the molecular engineering of the ancillary ligand. We have shown that the calculation results of the absorption spectra for these dyes using the PBE0 for the exchange-correlation functional are in better agreement with the experiment than using B3LYP or range-separated CAM-B3LYP. We have also derived a formula based on the DFT and used it to visually describe the level shifts in a solvent. The higher Jsc observed in these new dyes is explained by the fact that here, in contrast to N3, the excitation charge was effectively transferred to the anchoring ligand. Furthermore, we have shown that the difference dipole moment vectors of the ground and excited states can be used to determine the charge-transfer direction in an excitation process. Finally, different electron lifetimes observed in these dyes are explained by investigating the adsorption geometries and the relative orientations of iodine molecules in different "dyeI2" complexes.

Dye-Sensitized Solar Cells Employing Extracts from Four Cassia Flowers as Natural Sensitizers: Studies on Dye Ingredient Effect on Photovoltaic Performance

NASA Astrophysics Data System (ADS)

Maurya, Ishwar Chandra; Singh, Shalini; Neetu; Gupta, Arun Kumar; Srivastava, Pankaj; Bahadur, Lal

2018-01-01

Natural dyes extracted from four different flowers, namely, Cassia surattensis, Cassia tora, Cassia alata and Cassia occidentalis were used as sensitizers for TiO2-based dye-sensitized solar cells (DSSC). The dye extracts from flowers were obtained by a simple extraction technique and used without any further purification. Optical characteristics of dye extracts were studied. Fourier-transform infrared (FTIR) spectra were used to identify the constituents of extracted dyes. The photovoltaic performance of DSSC employing dye-capped TiO2 photoanodes was measured. The sensitization performance related to anchoring groups present and interaction between dyes with TiO2 surface is demonstrated. An attempt has been made to rationalize the observations by light absorption of the dye extracts and their adsorption on TiO2. The short-circuit current density ( I SC) values ranged from 0.06 mA/cm2 to 0.20 mA/cm2; open circuit voltage ( V OC) from 0.292 V to 0.833 V; fill factor (FF) from 0.7 to 0.9; efficiencies ( η) from 0.013% to 0.15% and incident photon-to-current conversion efficiency from 13% to 20%, were obtained for DSSC using these natural dye extracts. Cassia occidentalis showed the highest current density of 0.20 mA/cm2 and power conversion efficiency of 0.15%, which was due to better interaction between the carbonyl and hydroxyl group of the anthocyanin molecule of C. occidentalis and surface of TiO2 film. The red and blue shift of absorption wavelength of C. surattensis and the blue shift of absorption wavelength of the C. tora, C. alata and C. occidentalis extract in ethanol solution compared to that on TiO2 film has been used for the interpretation of obtained results.

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.

Estimation of ground and excited state dipole moment of laser dyes C504T and C521T using solvatochromic shifts of absorption and fluorescence spectra.

PubMed

Basavaraja, Jana; Suresh Kumar, H M; Inamdar, S R; Wari, M N

2016-02-05

The absorption and fluorescence spectra of laser dyes: coumarin 504T (C504T) and coumarin 521T (C521T) have been recorded at room temperature in a series of non-polar and polar solvents. The spectra of these dyes showed bathochromic shift with increasing in solvent polarity indicating the involvement of π→π⁎ transition. Kamlet-Taft and Catalan solvent parameters were used to analyze the effect of solvents on C504T and C521T molecules. The study reveals that both general solute-solvent interactions and specific interactions are operative in these two systems. The ground state dipole moment was estimated using Guggenheim's method and also by quantum mechanical calculations. The solvatochromic data were used to determine the excited state dipole moment (μ(e)). It is observed that dipole moment value of excited state (μ(e)) is higher than that of the ground state in both the laser dyes indicating that these dyes are more polar in nature in the excited state than in the ground state. Copyright © 2015. Published by Elsevier B.V.

Acridine orange--its use in the specific staining of DNA in mammalian tissue sections.

PubMed

Dutt, M K

1981-01-01

This paper reports on a new method for the use of acridine orange (AO) in an aqueous solution at pH 4.5 for staining DNA of rat tissue sections from which RNA has been extracted selectively with cold phosphoric acid. Not only this, AO can also be used as dye-SO2 reagent, prepared with NHCl and potassium metabisulphite, for staining DNA-aldehyde molecules of acid-hydrolysed tissue sections. AO samples, manufactured by the National Aniline Division as well as by G. T. Gurr have been used with equal success. Studies of stained sections under light microscope reveal the presence of specifically stained yellowish-orange nuclei. Those sections under fluorescent microscope with proper exciter and barrier filters reveal nuclei of maroon colour. The in situ absorption spectra of nuclei stained with AO-SO2 following acid-hydrolysis of tissue sections as well as those of nuclei stained with an aqueous solution of the dye following extraction of RNA have been presented herein. The mode of binding in the former case has been considered to be due to binding of the teritary amino group of the dye molecules with the DNA-aldehyde molecules and in the latter case to be due to electrostatic binding between the positively charged dye molecules with negatively charged phosphate groups of DNA. Implications of all these findings have been discussed.

Formation of trans-2-[4-(Dimethylamino)Styryl]-3-Ethyl-1,3-Benzothiazolium Perchlorate Dimers in the Presence of Sodium Polystyrene Sulfonate

NASA Astrophysics Data System (ADS)

Lavysh, A. V.; Maskevich, A. A.; Lugovskii, A. A.; Voropai, E. S.; Sulatskaya, A. I.; Kuznetsova, I. M.; Turoverov, K. K.

2017-01-01

The spectral properties of a novel thioflavin T derivative, trans-2-[4-(dimethylamino)styryl]-3-ethyl-1,3-benzothiazolium perchlorate (DMASEBT), were studied in aqueous solutions in the presence of sodium polystyrene sulfonate (SPS). It was shown that SPS either could interact with dye monomers or initiate the formation of non-fluorescent dye dimers depending on the concentration ratio of dye and polyelectrolyte. DMASEBT dimer formation in the presence of SPS produced a hypsochromic shift by 40 nm in the absorption spectrum and quenched fluorescence. A bathochromic shift of the absorption spectrum and an increase of the fluorescence intensity by an order of magnitude were observed if DMASEBT monomers interacted with SPS. Quantum-chemical analysis found that sandwich dimers (H-aggregates) were most stable. A comparison of DMASEBT spectra in the presence of SPS and amyloid fibrils showed that DMASEBT molecules were incorporated into amyloid fibrils as monomers. The spectral changes associated with this incorporation could not be explained by the formation of dye aggregates.

Photovoltaic studies of Dye Sensitized Solar cells Fabricated from Microwave Exposed Photo anodes

NASA Astrophysics Data System (ADS)

Ramachandran, Anju; Sreekala, C. O.; Sreelatha, K. S.; Jinchu, I.

2018-02-01

The configuration of Dye Sensitized solar cells (DSSC), consists of sintered nanoparticle titanium dioxide film, dyes, electrolyte and counter electrodes. Upon the absorption of photons by the dye molecules, excitons are generated, subsequently electrons are injected into the TiO2 photoanode. Afterward the electrons injected into the TiO2 photoanode, to produce photocurrent, scavenged by redox couple, and the hole transport to the photo cathode. The power conversion efficiency of the device depends on the amount of dye adsorbed by the photoanode. This paper explores in enhancing the efficiency of the device by controlled microwave exposure. With same exposure time, the photoanode is exposed at three different frequencies. SEM analysis is carried out to find the porosity of the photoanode on exposure. Current density is found to have an effect on microwave exposure.

Bio-Inspired Photon Absorption and Energy Transfer for Next Generation Photovoltaic Devices

NASA Astrophysics Data System (ADS)

Magsi, Komal

Nature's solar energy harvesting system, photosynthesis, serves as a model for photon absorption, spectra broadening, and energy transfer. Photosynthesis harvests light far differently than photovoltaic cells. These differences offer both engineering opportunity and scientific challenges since not all of the natural photon absorption mechanisms have been understood. In return, solar cells can be a very sensitive probe for the absorption characteristics of molecules capable of transferring charge to a conductive interface. The objective of this scientific work is the advancement of next generation photovoltaics through the development and application of natural photo-energy transfer processes. Two scientific methods were used in the development and application of enhancing photon absorption and transfer. First, a detailed analysis of photovoltaic front surface fluorescent spectral modification and light scattering by hetero-structure was conducted. Phosphor based spectral down-conversion is a well-known laser technology. The theoretical calculations presented here indicate that parasitic losses and light scattering within the spectral range are large enough to offset any expected gains. The second approach for enhancing photon absorption is based on bio-inspired mechanisms. Key to the utilization of these natural processes is the development of a detailed scientific understanding and the application of these processes to cost effective systems and devices. In this work both aspects are investigated. Dye type solar cells were prepared and tested as a function of Chlorophyll (or Sodium-Copper Chlorophyllin) and accessory dyes. Forster has shown that the fluorescence ratio of Chlorophyll is modified and broadened by separate photon absorption (sensitized absorption) through interaction with nearby accessory pigments. This work used the dye type solar cell as a diagnostic tool by which to investigate photon absorption and photon energy transfer. These experiments shed some doubt on the Foster Resonant Energy Transfer mechanism since energy relay dye architecture-photosensitizer mixtures do not broaden the response of solar cells. Spectral absorption characterization of chromophore-Chlorophyll solutions in varying solvent polarity confirm the lack of cooperative absorption via a Foster-like mechanism and point the way to new concepts of cooperative absorption in natural systems and the development of a new photovoltaic paradigm.

Photo-physical properties and triplet-triplet absorption of platinum(II) acetylides in solid PMMA matrices

NASA Astrophysics Data System (ADS)

Glimsdal, Eirik; Westlund, Robert; Lindgren, Mikael

2009-05-01

Because of their strong nonlinear optical properties, Platinum(II) acetylides are investigated as potential chromophores for optical power limiting (OPL) applications. The strong excited state absorption and efficient intersystem crossing to the triplet states in these materials are desired properties for good OPL performance. We recently reported on OPL and photo-physical properties of Pt(II)-acetylide chromophores in solution, modified with thiophenyl or triazole groups. [R. Westlund et al. J. Mater. Chem. 18, 166 (2008); E. Glimsdal et al. Proc. SPIE 6740, 67400M (2007)] The chromophores were later incorporated into poly(methyl-methacrylate) (PMMA) glasses. A variety of doped organic solids were prepared, reaching concentrations of up to 13 wt% of the guest molecule. Raman spectra of the doped solid devices proved that the chemical structure of the nonlinear dyes remains intact upon the polymerization of the solid matrix. Luminescence spectra confirm that the basic photo-physical properties (absorption, emission and inter-system crossing) observed for the solute molecules in THF are maintained also in the solid state. In particular, the phosphorescence lifetime stays in the order of μs to ms, just as in the oxygen evacuated liquid samples. Also, the wavelength dependence and time-dynamics of the triplet absorption spectra of the dyes, dissolved in THF solution and dispersed in solid PMMA matrices, were investigated and compared. Ground state UV absorption spectra between 300 and 420 nm have corresponding broad band visible triplet-triplet absorption between 400 and 800 nm. The triplet state extinction coefficients were determined to be in the order of 104 M-1cm-1.

Molecular engineering of fluorescein dyes as complementary absorbers in dye co-sensitized solar cells

DOE PAGES

Pepe, Giulio; Cole, Jacqueline M.; Waddell, Paul G.; ...

2016-09-22

Fluorescein dye derivatives exhibit extended optical absorption up to 500 nm, rendering these compounds suitable as co-absorbers in dye-sensitized solar cells (DSCs). A molecular engineering approach is presented, which embraces this intrinsic optical attribute of fluoresceins, while modifying the dye chemistry to enhance their light harvesting efficiency, in order to effectively tailor them for DSC applications. This approach first realizes relationships between the molecular structure and the optoelectronic properties for a series of five a priori known (parent) fluorescein dyes: 5-carboxyfluorescein (1), a mixture of m-carboxyfluorescein where m = 5 or 6 (2), 5-carboxyfluorescein diacetate (3), 6-carboxyfluorescein diacetate (4), amore » mixture of n-carboxy-2',7'-dichlorofluorescein diacetate where n = 5 or 6 (5). The first step in this approach combines, where available, experimental and computational methods so that electronic structure calculations can also be validated for representative fluorescein dyes. Such calculations can then be used reliably to predict the structure and properties of fluorescein dyes for cases where experimental data are lacking. Structure-function relationships established from this initial step inform the selection of parent dye 1 that is taken forward to the second step in molecular engineering: in silico chemical derivation to re-functionalize 1 for DSC applications. For this purpose, computational calculations are used to extend the charge conjugation in 1 between its donor and acceptor moieties. These structural modifications result in a bathochromic shift of the lowest excitation by ~1.3-1.9 eV (100-170 nm), making the dye optically absorb in the visible region. Further calculations on dye molecules adsorbed onto the surface of a TiO 2 cluster are used to investigate the dye sensitization behavior via dye adsorption energies and anchoring modes. The results of this theoretical investigation lead to two molecularly engineered fluoresceins being proposed to act as co-sensitizers together with a rhodamine dye. This combination of three dyes ensures chemical compatibility, panchromatic absorption, and restores optical absorption dipping otherwise observed in a DSC device at ~350-400 nm owing to the I-/I- 3 electrolyte. Altogether, the results of this study demonstrate that molecular engineering can be used to identify suitable chemical modifications for organic dyes with improved light harvesting properties for photovoltaic applications.« less

Molecular engineering of fluorescein dyes as complementary absorbers in dye co-sensitized solar cells

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

Pepe, Giulio; Cole, Jacqueline M.; Waddell, Paul G.

Fluorescein dye derivatives exhibit extended optical absorption up to 500 nm, rendering these compounds suitable as co-absorbers in dye-sensitized solar cells (DSCs). A molecular engineering approach is presented, which embraces this intrinsic optical attribute of fluoresceins, while modifying the dye chemistry to enhance their light harvesting efficiency, in order to effectively tailor them for DSC applications. This approach first realizes relationships between the molecular structure and the optoelectronic properties for a series of five a priori known (parent) fluorescein dyes: 5-carboxyfluorescein (1), a mixture of m-carboxyfluorescein where m = 5 or 6 (2), 5-carboxyfluorescein diacetate (3), 6-carboxyfluorescein diacetate (4), amore » mixture of n-carboxy-2',7'-dichlorofluorescein diacetate where n = 5 or 6 (5). The first step in this approach combines, where available, experimental and computational methods so that electronic structure calculations can also be validated for representative fluorescein dyes. Such calculations can then be used reliably to predict the structure and properties of fluorescein dyes for cases where experimental data are lacking. Structure-function relationships established from this initial step inform the selection of parent dye 1 that is taken forward to the second step in molecular engineering: in silico chemical derivation to re-functionalize 1 for DSC applications. For this purpose, computational calculations are used to extend the charge conjugation in 1 between its donor and acceptor moieties. These structural modifications result in a bathochromic shift of the lowest excitation by ~1.3-1.9 eV (100-170 nm), making the dye optically absorb in the visible region. Further calculations on dye molecules adsorbed onto the surface of a TiO 2 cluster are used to investigate the dye sensitization behavior via dye adsorption energies and anchoring modes. The results of this theoretical investigation lead to two molecularly engineered fluoresceins being proposed to act as co-sensitizers together with a rhodamine dye. This combination of three dyes ensures chemical compatibility, panchromatic absorption, and restores optical absorption dipping otherwise observed in a DSC device at ~350-400 nm owing to the I-/I- 3 electrolyte. Altogether, the results of this study demonstrate that molecular engineering can be used to identify suitable chemical modifications for organic dyes with improved light harvesting properties for photovoltaic applications.« less

Dye-Incorporated Polynaphthalenediimide Acceptor for Additive-Free High-Performance All-Polymer Solar Cells.

PubMed

Chen, Dong; Yao, Jia; Chen, Lie; Yin, Jingping; Lv, Ruizhi; Huang, Bin; Liu, Siqi; Zhang, Zhi-Guo; Yang, Chunhe; Chen, Yiwang; Li, Yongfang

2018-04-16

All-polymer solar cells (all-PSCs) can offer unique advantages for applications in flexible devices, and naphthalene diimide (NDI)-based polymer acceptors are the widely used polymer acceptors. However, their power conversion efficiency (PCE) still lags behind that of state-of-the-art polymer solar cells, due to low light absorption, suboptimal energy levels and the strong aggregation of the NDI-based polymer acceptor. Herein, a rhodanine-based dye molecule was introduced into the NDI-based polymer acceptor by simple random copolymerization and showed an improved light absorption coefficient, an up-shifted lowest unoccupied molecular orbital level and reduced crystallization. Consequently, additive-free all-PSCs demonstrated a high PCE of 8.13 %, which is one of the highest performance characteristics reported for all-PSCs to date. These results indicate that incorporating a dye into the n-type polymer gives insight into the precise design of high-performance polymer acceptors for all-PSCs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast electron and energy transfer in dye-sensitized iron oxide and oxyhydroxide nanoparticles.

PubMed

Gilbert, Benjamin; Katz, Jordan E; Huse, Nils; Zhang, Xiaoyi; Frandsen, Cathrine; Falcone, Roger W; Waychunas, Glenn A

2013-10-28

An emerging area in chemical science is the study of solid-phase redox reactions using ultrafast time-resolved spectroscopy. We have used molecules of the photoactive dye 2',7'-dichlorofluorescein (DCF) anchored to the surface of iron(III) oxide nanoparticles to create iron(II) surface atoms via photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(III) oxide nanoparticles has not been reported. We addressed this topic by performing femtosecond transient absorption (TA) measurements of aqueous suspensions of uncoated and DCF-sensitized iron oxide and oxyhydroxide nanoparticles, and an aqueous iron(III)-dye complex. Following light absorption, excited state relaxation times of the dye of 115-310 fs were found for all samples. Comparison between TA dynamics on uncoated and dye-sensitized hematite nanoparticles revealed the dye de-excitation pathway to consist of a competition between electron and energy transfer to the nanoparticles. We analyzed the TA data for hematite nanoparticles using a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye-oxide energy transfer is energetically forbidden) even though the acceptor states are different. Comparison of the alignment of the excited states of the dye and the unoccupied states of these oxides showed that the dye injects into acceptor states of different symmetry (Ti t2gvs. Fe eg).

Wavelength dependence and multiple-induced states in photoresponses of copper phthalocyanine-doped gold nanoparticle single-electron device

NASA Astrophysics Data System (ADS)

Yamamoto, Makoto; Ueda, Rieko; Terui, Toshifumi; Imazu, Keisuke; Tamada, Kaoru; Sakano, Takeshi; Matsuda, Kenji; Ishii, Hisao; Noguchi, Yutaka

2014-01-01

We have proposed a gold nanoparticle (GNP)-based single-electron transistor (SET) doped with a dye molecule, where the molecule works as a photoresponsive floating gate. Here, we examined the source-drain current (I_{\\text{SD}}) at a constant drain voltage under light irradiation with various wavelengths ranging from 400 to 700 nm. Current change was enhanced at the wavelengths of 600 and 700 nm, corresponding to the optical absorption band of the doped molecule (copper phthalocyanine: CuPc). Moreover, several peaks appear in the histograms of I_{\\text{SD}} during light irradiation, indicating that multiple discrete states were induced in the device. The results suggest that the current change was initiated by the light absorption of CuPc and multiple CuPc molecules near the GNP working as a floating gate. Molecular doping can activate advanced device functions in GNP-based SETs.

Dendrimer-based Nanoparticle for Dye Sensitized Solar Cells with Improved Efficiency.

PubMed

Ghann, William; Kang, Hyeonggon; Uddin, Jamal; Gonawala, Sunalee J; Mahatabuddin, Sheikh; Ali, Meser M

2018-01-01

Dye sensitized solar cells were fabricated with DyLight680 (DL680) dye and its corresponding europium conjugated dendrimer, DL680-Eu-G5PAMAM, to study the effect of europium on the current and voltage characteristics of the DL680 dye sensitized solar cell. The dye samples were characterized by using Absorption Spectroscopy, Emission Spectroscopy, Fluorescence lifetime and Fourier Transform Infrared measurements. Transmission electron microscopy imaging was carried out on the DL680-Eu-G5PAMAM dye and DL680-Eu-G5PAMAM dye sensitized titanium dioxide nanoparticles to analyze the size of the dye molecules and examine the interaction of the dye with titanium dioxide nanoparticles. The DL680-Eu-G5PAMAM dye sensitized solar cells demonstrated an enhanced solar-to-electric energy conversion of 0.32% under full light illumination (100 mWcm -2 , AM 1.5 Global) in comparison with that of DL680 dye sensitized cells which recorded an average solar-to-electric energy conversion of only 0.19%. The improvement of the efficiency could be due to the presence of the europium that enhances the propensity of dye to absorb sunlight.

Resonance Energy Transfer between Carbon Monoxide and Oxygen Molecules Using Dye Laser Intracavity Absorption Spectroscopy.

DTIC Science & Technology

1987-10-21

intensity changes. Greater sensitivity over single-pass measurements make this technique for observing absorption spectra more desireable. The absorber...resulting in a resolution (A) of about 0.037 A. The signal was focused onto an array of 500 detector elements in the vidicon. Because the width of each... detector is only 0.001 inch, there is a "cross talk" effect 5 between adjacent elements which lowers the resolution to about 0.074 A. Under this

Porous Silicon Covered with Silver Nanoparticles as Surface-Enhanced Raman Scattering (SERS) Substrate for Ultra-Low Concentration Detection.

PubMed

Kosović, Marin; Balarin, Maja; Ivanda, Mile; Đerek, Vedran; Marciuš, Marijan; Ristić, Mira; Gamulin, Ozren

2015-12-01

Microporous and macro-mesoporous silicon templates for surface-enhanced Raman scattering (SERS) substrates were produced by anodization of low doped p-type silicon wafers. By immersion plating in AgNO3, the templates were covered with silver metallic film consisting of different silver nanostructures. Scanning electron microscopy (SEM) micrographs of these SERS substrates showed diverse morphology with significant difference in an average size and size distribution of silver nanoparticles. Ultraviolet-visible-near-infrared (UV-Vis-NIR) reflection spectroscopy showed plasmonic absorption at 398 and 469 nm, which is in accordance with the SEM findings. The activity of the SERS substrates was tested using rhodamine 6G (R6G) dye molecules and 514.5 nm laser excitation. Contrary to the microporous silicon template, the SERS substrate prepared from macro-mesoporous silicon template showed significantly broader size distribution of irregular silver nanoparticles as well as localized surface plasmon resonance closer to excitation laser wavelength. Such silver morphology has high SERS sensitivity that enables ultralow concentration detection of R6G dye molecules up to 10(-15) M. To our knowledge, this is the lowest concentration detected of R6G dye molecules on porous silicon-based SERS substrates, which might even indicate possible single molecule detection.

Insights into the Mechanism of a Covalently Linked Organic Dye-Cobaloxime Catalyst System for Dye-Sensitized Solar Fuel Devices.

PubMed

Pati, Palas Baran; Zhang, Lei; Philippe, Bertrand; Fernández-Terán, Ricardo; Ahmadi, Sareh; Tian, Lei; Rensmo, Håkan; Hammarström, Leif; Tian, Haining

2017-06-09

A covalently linked organic dye-cobaloxime catalyst system based on mesoporous NiO is synthesized by a facile click reaction for mechanistic studies and application in a dye-sensitized solar fuel device. The system is systematically investigated by photoelectrochemical measurements, density functional theory, time-resolved fluorescence, transient absorption spectroscopy, and photoelectron spectroscopy. The results show that irradiation of the dye-catalyst on NiO leads to ultrafast hole injection into NiO from the excited dye, followed by a fast electron transfer process to reduce the catalyst. Moreover, the dye adopts different structures with different excited state energies, and excitation energy transfer occurs between neighboring molecules on the semiconductor surface. The photoelectrochemical experiments also show hydrogen production by this system. The axial chloride ligands of the catalyst are released during photocatalysis to create the active sites for proton reduction. A working mechanism of the dye-catalyst system on the photocathode is proposed on the basis of this study. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Spectroscopic (FT-IR, FT-Raman and UV-Visible) investigations, NMR chemical shielding anisotropy (CSA) parameters of 2,6-Diamino-4-chloropyrimidine for dye sensitized solar cells using density functional theory.

PubMed

Gladis Anitha, E; Joseph Vedhagiri, S; Parimala, K

2015-02-05

The molecular structure, geometry optimization, vibrational frequencies of organic dye sensitizer 2,6-Diamino-4-chloropyrimidine (DACP) were studied based on Hartree-Fock (HF) and density functional theory (DFT) using B3LYP methods with 6-311++G(d,p) basis set. Ultraviolet-Visible (UV-Vis) spectrum was investigated by time dependent DFT (TD-DFT). Features of the electronic absorption spectrum in the UV-Visible regions were assigned based on TD-DFT calculation. The absorption bands are assigned to transitions. The interfacial electron transfer between semiconductor TiO2 electrode and dye sensitizer DACP is due to an electron injection process from excited dye to the semiconductor's conduction band. The observed and the calculated frequencies are found to be in good agreement. The energies of the frontier molecular orbitals (FMOS) have also been determined. The chemical shielding anisotropic (CSA) parameters are calculated from the NMR analysis, Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Copyright © 2014 Elsevier B.V. All rights reserved.

Aggregation Properties and Liquid Crystal Phase of a Dye Based on Naphthalenetetracarboxylic Acid

NASA Astrophysics Data System (ADS)

Tomasik, Michelle; Collings, Peter

2007-03-01

R003 is a dye produced for thin film optical components by Optiva, Inc.^1 made from the sulfonation of the dibenzimidazole derivative of naphthalenetetracarboxylic acid. Its molecular structure is very different from the aggregating food dye previously investigated in our laboratory^2 and R003 forms a liquid crystal phase at significantly lower concentrations. We have performed polarizing microscopy, absorption spectroscopy, and x-ray diffraction experiments in order to determine the phase diagram and aggregate structure. In addition, we have included both translational and orientational entropy in the theoretical analysis of the aggregation process, and have used a more realistic lineshape in analyzing the absorption data. Our results indicate that the ``bond energy'' for molecules in an aggregate is even larger than for the previously studied dye and that the aggregate structure has a cross-sectional area equal to two or three molecular areas rather than one.^1Lazarev, P., N. Ovchinnikova, M. Paukshto, SID Int. Symp. Digest of Tech. Papers, San Jose, California, June XXXII, 571 (2001).^2V. R. Horowitz, L. A. Janowitz, A. L. Modic, P. A. Heiney, and P. J. Collings, Phys. Rev. E 72, 041710 (2005).

Experimental and theoretical simulation studies on picosecond closed-aperture Z-scan profiles of N,N‧-Bis(2,5,-di-tert-butylphenyl)-3,4,9,10-perylenedicarboximide (DBPI)

NASA Astrophysics Data System (ADS)

Tripathy, Umakanta; Rallabandi, Sailaja; Bisht, Prem B.

2017-10-01

The optical nonlinear refractive and absorptive parameters of the dye N,N‧-Bis(2,5,-di-tert-butylphenyl)-3,4,9,10-perylenedicarboximide (DBPI) in 96% sulphuric acid have been obtained by a single closed-aperture (CA) Z-scan technique with picosecond pulses at the wavelength of 532 nm. Here a theoretical model was used to deduce both the refractive and absorptive optical nonlinearity present simultaneously in the CA Z-scan profile. Under the range of concentrations and energies studied here, we found that the effect of saturable absorption (SA) is dominating at higher concentrations (i.e. 1.0 × 10-3 M), whereas the reverse saturable absorption (RSA) effect was taken over at dilute concentrations (i.e. 1.0 × 10-4 M and 1.0 × 10-5 M). The dominance of absorptive nonlinearity over the refractive nonlinearity results in a low value of the refractive cross-section (σr). A relative increase in the value of σr is observed with decrease in the dye concentration. Mathematical modeling of CA Z-scan profiles of DBPI shows the existence of peak-valley or valley-peak structure depending upon the contribution of nonlinear absorption. The optical nonlinear parameters have also been estimated by theoretical simulation studies as a function of wavelength and compared with the experimental results. The dye DBPI has been found to be suitable as an important highly photostable molecule for photonic devices in the visible region (400-630 nm).

Near-infrared optical-absorption behavior in high-beta nonlinear optical chromophore-polymer guest-host materials. II. Dye spacer length effects in an amorphous polycarbonate copolymer host

NASA Astrophysics Data System (ADS)

Barto, Richard R.; Frank, Curtis W.; Bedworth, Peter V.; Ermer, Susan; Taylor, Rebecca E.

2005-06-01

In the second of a three-part series, spectral absorption behavior of nonlinear optical (NLO) dyes incorporated into amorphous polycarbonate, comprised of a homologous series of dialkyl spacer groups extending from the midsection of the dye molecule, is characterized by UV-Vis and photothermal deflection spectroscopy. The dyes are structural analogs of the NLO dye FTC [2-(3-cyano-4-{2-[5-(2-{4-[ethyl-(2-methoxyethyl)amino]phenyl}vinyl)-3,4-diethylthiophen-2-yl]vinyl}-5,5-dimethyl-5H-furan-2-ylidene)malononitrile]. Previous Monte Carlo calculations [B. H. Robinson and L. R. Dalton, J. Phys. Chem. A 104, 4785 (2000)] predict a strong dependence of the macroscopic nonlinear optical susceptibility on the chromophore waist: length aspect ratio in electric-field-poled films arising from interactions between chromophores. It is expected that these interactions will play a role in the absorption characteristics of unpoled films, as well. The spacer groups range in length from diethyl to dihexyl, and each dye is studied over a wide range of concentrations. Among the four dyes studied, a universal dependence of near-IR loss on inhomogeneous broadening of the dye main absorption peak is found. The inhomogeneous width and its concentration dependence are seen to vary with spacer length in a manner characteristic of the near-IR loss-concentration slope at transmission wavelengths of 1.06 and 1.3μm, but not at 1.55μm. The lower wavelength loss behavior is assigned to purely Gaussian broadening, and is described by classical mixing thermodynamic quantities based on the Marcus theory of inhomogeneous broadening [R. A. Marcus, J. Chem. Phys. 43, 1261 (1965)], modeled as a convolution of dye-dye dipole broadening and dye-polymer van der Waals broadening. The Gaussian dipole interactions follow a Loring dipole-broadening description [R. F. Loring, J. Phys. Chem. 94, 513 (1990)] dominated by the excited-state dipole moment, and have a correlated homogeneous broadening contribution. The long-wavelength loss behavior has a non-Gaussian dye-dye dipole contribution which follows Kador's broadening analysis [L. Kador, J. Chem. Phys. 95, 5574 (1991)], with a net broadening described by a convolution of this term with a Gaussian van der Waals interaction given by Obata et al. [M. Obata, S. Machida, and K. Horie, J. Polym. Sci. B 37, 2173 (1999)], with each term governed by the dye spacer length. A minimum in broadening and loss-concentration slope at a spacer length of four carbons per alkyl at all wavelengths has important consequences for practical waveguide devices, and is of higher aspect ratio than the spherical limit shown by Robinson and Dalton to minimize dipole interactions under a poling field.

Solvent dependent triphenylamine based D-(pi-A)n type dye molecules and optical properties.

PubMed

Li, Xiaochuan; Son, Young-A; Kim, Young-Sung; Kim, Sung-Hoon; Kun, Jun; Shin, Jong-Il

2012-02-01

D-(pi-A)n type dyes of triphenylamine derivatives were synthesized and their absorption and luminescence in different solvents were examined to investigate solvent dependent properties observed for their emissions in solvents with different dielectric constants. The emission wavelengths showed a dramatic blue shift with increasing solvent polarity. The results of molecular orbital calculations by computer simulation, based on Material Studio suite of programs, were found to reasonably account for the spectral properties. Relative levels of HOMO and LUMO were measured and calculated and all derivatives exhibited strong solid fluorescence with distinctively different FWHMs.

First-principles calculation of the optical properties of an amphiphilic cyanine dye aggregate.

PubMed

Haverkort, Frank; Stradomska, Anna; de Vries, Alex H; Knoester, Jasper

2014-02-13

Using a first-principles approach, we calculate electronic and optical properties of molecular aggregates of the dye amphi-pseudoisocyanine, whose structures we obtained from molecular dynamics (MD) simulations of the self-aggregation process. Using quantum chemistry methods, we translate the structural information into an effective time-dependent Frenkel exciton Hamiltonian for the dominant optical transitions in the aggregate. This Hamiltonian is used to calculate the absorption spectrum. Detailed analysis of the dynamic fluctuations in the molecular transition energies and intermolecular excitation transfer interactions in this Hamiltonian allows us to elucidate the origin of the relevant time scales; short time scales, on the order of up to a few hundreds of femtoseconds, result from internal motions of the dye molecules, while the longer (a few picosecond) time scales we ascribe to environmental motions. The absorption spectra of the aggregate structures obtained from MD feature a blue-shifted peak compared to that of the monomer; thus, our aggregates can be classified as H-aggregates, although considerable oscillator strength is carried by states along the entire exciton band. Comparison to the experimental absorption spectrum of amphi-PIC aggregates shows that the simulated line shape is too wide, pointing to too much disorder in the internal structure of the simulated aggregates.

Clay induced aggregation of a tetra-cationic metalloporphyrin in Layer by Layer self assembled film

NASA Astrophysics Data System (ADS)

Banik, Soma; Bhattacharjee, J.; Hussain, S. A.; Bhattacharjee, D.

2015-12-01

Porphyrins have a general tendency to form aggregates in ultrathin films. Also electrostatic adsorption of cationic porphyrins onto anionic nano clay platelets results in the flattening of porphyrin moieties. The flattening is evidenced by the red-shifting of Soret band with respect to the aqueous solution. In the present communication, we have studied the clay induced aggregation behaviour of a tetra-cationic metalloporphyrin Manganese (III) 5, 10, 15, 20-tetra (4 pyridyl)-21 H, 23 H-porphine chloride tetrakis (methochloride) (MnTMPyP) in Layer-by-Layer (LbL) self assembled film. The adsorption of dye molecules onto nano clay platelets resulted in the flattening of the meso substituent groups of the dye chromophore. In Layer-by-Layer ultrathin film, the flattened porphyrin molecules tagged nano clay platelets were further associated to form porphyrin aggregates. This has been clearly demonstrated from the UV-vis absorption spectroscopic studies. Atomic Force Microscopic (AFM) studies gave visual evidence of the association of organo-clay hybrid molecules in the LbL film.

Dye-sensitized solar cell employing zinc oxide aggregates grown in the presence of lithium

DOEpatents

Zhang, Qifeng; Cao, Guozhong

2013-10-15

Provided are a novel ZnO dye-sensitized solar cell and method of fabricating the same. In one embodiment, deliberately added lithium ions are used to mediate the growth of ZnO aggregates. The use of lithium provides ZnO aggregates that have advantageous microstructure, morphology, crystallinity, and operational characteristics. Employing lithium during aggregate synthesis results in a polydisperse collection of ZnO aggregates favorable for porosity and light scattering. The resulting nanocrystallites forming the aggregates have improved crystallinity and more favorable facets for dye molecule absorption. The lithium synthesis improves the surface stability of ZnO in acidic dyes. The procedures developed and disclosed herein also help ensure the formation of an aggregate film that has a high homogeneity of thickness, a high packing density, a high specific surface area, and good electrical contact between the film and the fluorine-doped tin oxide electrode and among the aggregate particles.

Degradation mechanism of Direct Pink 12B treated by iron-carbon micro-electrolysis and Fenton reaction.

PubMed

Wang, Xiquan; Gong, Xiaokang; Zhang, Qiuxia; Du, Haijuan

2013-12-01

The Direct Pink 12B dye was treated by iron-carbon micro-electrolysis (ICME) and Fenton oxidation. The degradation pathway of Direct Pink 12B dye was inferred by ultraviolet visible (UV-Vis), infrared absorption spectrum (IR) and high performance liquid chromatography-mass spectrometry (HPLC-MS). The major reason of decolorization was that the conjugate structure was disrupted in the iron-carbon micro-electrolysis (ICME) process. However, the dye was not degraded completely because benzene rings and naphthalene rings were not broken. In the Fenton oxidation process, the azo bond groups surrounded by higher electron cloud density were first attacked by hydroxyl radicals to decolorize the dye molecule. Finally benzene rings and naphthalene rings were mineralized to H2O and CO2 under the oxidation of hydroxyl radicals. Copyright © 2013 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Kinetics of leather dyeing pretreated with enzymes: role of acid protease.

PubMed

Kanth, Swarna Vinodh; Venba, Rajangam; Jayakumar, Gladstone Christopher; Chandrababu, Narasimhan Kannan

2009-04-01

In the present investigation, kinetics of dyeing involving pretreatment with acid protease has been presented. Application of acid protease in dyeing process resulted in increased absorption and diffusion of dye into the leather matrix. Enzyme treatment at 1% concentration, 60 min duration and 50 degrees C resulted in maximum of 98% dye exhaustion and increased absorption rate constants. The final exhaustion (C(infinity)) for the best fit of CI Acid Black 194 dye has been 98.5% with K and r2 values from the modified Cegarra-Puente isotherm as 0.1033 and 0.0631. CI Acid Black 194 being a 2:1 metal complex acid dye exhibited higher absorption rate than the acid dye CI Acid Black 210. A reduction in 50% activation energy calculated from Arrhenius equation has been observed in enzyme assisted dyeing process of both the dyes that substantiates enhanced dye absorption. The absorption rate constant calculated with modified Cegarra-Puente equation confirm higher rate constants and faster kinetics for enzyme assisted dyeing process. Enzyme treated leather exhibited richness of color and shade when compared with control. The present study substantiates the essential role of enzyme pretreatment as an eco-friendly leather dyeing process.

Collison-Induced Absorption of Oxygen Molecule as Studied by High Sensitivity Spectroscopy

NASA Astrophysics Data System (ADS)

Kashihara, Wataru; Shoji, Atsushi; Kawai, Akio

2017-06-01

Oxygen dimol is transiently generated when two oxygen molecules collide. At this short period, the electron clouds of molecules are distorted and some forbidden transition electronic transitions become partially allowed. This transition is called CIA (Collision-induced absorption). There are several CIA bands appearing in the spectral region from UV to near IR. Absorption of solar radiation by oxygen dimol is a small but significant part of the total budget of incoming shortwave radiation. However, a theory predicting the lineshape of CIA is still under developing. In this study, we measured CIA band around 630 nm that is assigned to optical transition, a^{1}Δ_{g}(v=0):a^{1}Δ_{g}(v=0)-X^{3}Σ_{g}^{-}(v=0):X^{3}Σ_{g}^{-}(v=0) of oxygen dimol. CRDS(Cavity Ring-down Spectroscopy) was employed to measure weak absorption CIA band of oxygen. Laser beam around 630 nm was generated by a dye laser that was pumped by a YAG Laser. Multiple reflection of the probe light was performed within a vacuum chamber that was equipped with two high reflective mirrors. We discuss the measured line shape of CIA on the basis of collision pair model.

DFT study of the effect of substituents on the absorption and emission spectra of Indigo

PubMed Central

2012-01-01

Background Theoretical analyses of the indigo dye molecule and its derivatives with Chlorine (Cl), Sulfur (S), Selenium (Se) and Bromine (Br) substituents, as well as an analysis of the Hemi-Indigo molecule, were performed using the Gaussian 03 software package. Results Calculations were performed based on the framework of density functional theory (DFT) with the Becke 3- parameter-Lee-Yang-Parr (B3LYP) functional, where the 6-31 G(d,p) basis set was employed. The configuration interaction singles (CIS) method with the same basis set was employed for the analysis of excited states and for the acquisition of the emission spectra. Conclusions The presented absorption and emission spectra were affected by the substitution position. When a hydrogen atom of the molecule was substituted by Cl or Br, practically no change in the absorbed and emitted energies relative to those of the indigo molecule were observed; however, when N was substituted by S or Se, the absorbed and emitted energies increased. PMID:22809100

Anisotropy in Third-Order Nonlinear Optical Susceptibility of a Squarylium Dye in a Nematic Liquid Crystal

NASA Astrophysics Data System (ADS)

Jin, Zhao-Hui; Li, Zhong-Yu; Kasatani, Kazuo; Okamoto, Hiroaki

2006-03-01

A squarylium dye is dissolved in 4-cyano-4'-pentylbiphenyl (5CB) and oriented by sandwiching mixtures between two pieces of rubbed glass plates. The optical absorption spectra of the oriented squarylium dye-5CB layers exhibit high anisotropy. The third-order nonlinear optical responses and susceptibilities χ(3)e of squarylium dye in 5CB are measured with light polarizations parallel and perpendicular to the orientational direction by the resonant femtosecond degenerate four-wave mixing (DFWM) technique. Temporal profiles of the DFWM signal of the oriented squarylium dye-5CB layers with light polarizations parallel and perpendicular to the orientational direction are measured with a time resolution of 0.3 ps (FWHM), and are found to consist of two components, i.e., the coherent instantaneous nonlinear response and slow response due to the formation of excited molecules. A high anisotropic ratio of χ(3)e, 10.8±1.2, is observed for the oriented layers.

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

Interaction of light with dye-doped calcium phosphate nanoparticles

NASA Astrophysics Data System (ADS)

Russin, Timothy John

In this work we present work on a novel amorphous calcium phosphate nanoparticle system for use in bioimaging and drug delivery applications. The system, by virtue of its synthesis, can be made to encapsulate and protect any number of molecules that are not suitable for biological applications on their own; for example, medication that is poorly soluble in aqueous solution can be encapsulated for delivery, or fragile optical molecules can be encapsulated to protect them from the local environment. We have encapsulated the near-infrared dye indocyanine green, which has beneficial properties for optical imaging (low biotoxicity, absorption and emission at a minimum of tissue absorption). There are two original works presented in this thesis. The first describes the measurement of the quantum yield of the indocyanine green-doped nanoparticles, as well as the development of a theoretical method to extract the molecular quantum yield of a fluorophore encapsulated in a dielectric sphere from effective quantum yield measurements of nanoparticle dispersions in solution. The second work is an application of diffuse scattering theory to the problem of light propagation in biological tissue; specifically, the limits on penetration depth for photodynamic therapy and bioimaging.

Charge transfer from an adsorbed ruthenium-based photosensitizer through an ultra-thin aluminium oxide layer and into a metallic substrate

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

Gibson, Andrew J.; Temperton, Robert H.; Handrup, Karsten

2014-06-21

The interaction of the dye molecule N3 (cis-bis(isothiocyanato)bis(2,2-bipyridyl-4,4′-dicarbo-xylato) -ruthenium(II)) with the ultra-thin oxide layer on a AlNi(110) substrate, has been studied using synchrotron radiation based photoelectron spectroscopy, resonant photoemission spectroscopy, and near edge X-ray absorption fine structure spectroscopy. Calibrated X-ray absorption and valence band spectra of the monolayer and multilayer coverages reveal that charge transfer is possible from the molecule to the AlNi(110) substrate via tunnelling through the ultra-thin oxide layer and into the conduction band edge of the substrate. This charge transfer mechanism is possible from the LUMO+2 and 3 in the excited state but not from the LUMO,more » therefore enabling core-hole clock analysis, which gives an upper limit of 6.0 ± 2.5 fs for the transfer time. This indicates that ultra-thin oxide layers are a viable material for use in dye-sensitized solar cells, which may lead to reduced recombination effects and improved efficiencies of future devices.« less

Dynamic evolution of light-induced orientation of dye-doped liquid crystals in liquid phase studied by time-resolved optically heterodyned optical Kerr effect technique.

PubMed

Yang, Pei; Liu, Liying; Xu, Lei

2008-02-28

Transient evolution of light-induced molecular reorientation both in 1-amino-anthraquinone (1AAQ) dye and azobenzene doped isotropic liquid crystals (LCs) were studied by time-resolved optically heterodyned optical Kerr effect method. The results give clear direct experimental proof that under short pulse (30 ps) excitation, LC molecules orientate toward the excitation light polarization direction in the 1AAQ/LC system. However, LC molecular orientation becomes orthogonal to the light polarization in azobenzene/LC system. Time-resolved excited-state absorption of 1AAQ and wavelength dependent excited-state absorption of azobenzene were also observed and their contributions to the early dynamics of the third order optical responses of the two systems were confirmed. A simplified two-level mean-field theory was derived to reveal the intensity dependence of orientation enhancement factor in azobenzene/LC system considering the photoisomerization process.

Energy and charge transfer in nanoscale hybrid materials.

PubMed

Basché, Thomas; Bottin, Anne; Li, Chen; Müllen, Klaus; Kim, Jeong-Hee; Sohn, Byeong-Hyeok; Prabhakaran, Prem; Lee, Kwang-Sup

2015-06-01

Hybrid materials composed of colloidal semiconductor quantum dots and π-conjugated organic molecules and polymers have attracted continuous interest in recent years, because they may find applications in bio-sensing, photodetection, and photovoltaics. Fundamental processes occurring in these nanohybrids are light absorption and emission as well as energy and/or charge transfer between the components. For future applications it is mandatory to understand, control, and optimize the wide parameter space with respect to chemical assembly and the desired photophysical properties. Accordingly, different approaches to tackle this issue are described here. Simple organic dye molecules (Dye)/quantum dot (QD) conjugates are studied with stationary and time-resolved spectroscopy to address the dynamics of energy and ultra-fast charge transfer. Micellar as well as lamellar nanostructures derived from diblock copolymers are employed to fine-tune the energy transfer efficiency of QD donor/dye acceptor couples. Finally, the transport of charges through organic components coupled to the quantum dot surface is discussed with an emphasis on functional devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Function of CN group in organic sensitizers: The first principle study.

PubMed

Liu, Yun; Shao, Di; Bai, Xiaohui; Yang, Zhenqing; Lin, Chundan; Shao, Changjin

2017-05-15

The cyano group (CN) of the acceptor in organic sensitizers plays an important role for highly efficient dye-sensitized solar cells. In this paper, three 5, 6-difluoro-2,1,3-benzothiadiazole (DFBTD) organic molecules with different number of CN units, named ME15, ME16 and ME17, were investigated by the density functional theory (DFT) and time-dependent DFT (TDDFT). We analyzed the CNs effects on the electronic structures, optical properties, adsorption modes and electron transfer and injection. The result shows that ME17 has the largest maximum absorption wavelength (λ max ) among these new designed dyes due to the strong electron withdrawing ability of two CNs. In addition, CN greatly influence the adsorption modes of dye/TiO 2 and electron injection mechanism. ME16 with one CN also has good optical absorption properties and its acceptor has the strongest coupling strength with the TiO 2 semiconductor which is favorable for electron transfer and injection. Thus, we believe that the number of CN groups in acceptor should be moderate and one CN in D-A-π-A structure dyes may be the more appropriate focusing on the light harvesting ability, electron transfer and electron injection. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Interaction of thioflavin T with amyloid fibrils: stoichiometry and affinity of dye binding, absorption spectra of bound dye.

PubMed

Sulatskaya, Anna I; Kuznetsova, Irina M; Turoverov, Konstantin K

2011-10-06

The fluorescence of the benzothiazole dye thioflavin T (ThT) is a well-known test for amyloid fibril formation. It has now become evident that ThT can also be used for structural investigations of amyloid fibrils and even for the treatment of amyloid diseases. In this case, one of the most urgent problems is an accurate determination of ThT-amyloid fibril binding parameters: the number of binding modes, stoichiometry, and binding constant for each mode. To obtain information concerning the ThT-amyloid fibril binding parameters, we propose to use absorption spectrophotometry of solutions prepared by equilibrium microdialysis. This approach is inherently designed for the determination of dye-receptor binding parameters. However, it has been very rarely used in the study of dye-protein interactions and has never been used to study the binding parameters of ThT or its analogues to amyloid fibrils. We showed that, when done in corpore, this approach enables the determination of not only binding parameters but also the absorption spectrum and molar extinction coefficient of ThT bound to sites of different binding modes. The proposed approach was used for the examination of lysozyme amyloid fibrils. Two binding modes were found for the ThT-lysozyme amyloid fibril interaction. These binding modes have significantly different binding constants (K(b1) = 7.5 × 10(6) M(-1), K(b2) = 5.6 × 10(4) M(-1)) and a different number of dye binding sites on the amyloid fibrils per protein molecule (n(1) = 0.11, n(2) = 0.24). The absorption spectra of ThT bound to sites of different modes differ from each other (ε(b1,max) = 5.1 × 10(4) M(-1) cm(-1), ε(b2,max) = 6.7 × 10(4) M(-1)cm(-1), λ(max) = 449 nm) and significantly differ from that of free ThT in aqueous solution (ε(max) = 3.2 × 10(4) M(-1)cm(-1), λ(max) = 412 nm). © 2011 American Chemical Society

Organic fluorescent dye-based nanomaterials: Advances in the rational design for imaging and sensing applications.

PubMed

Svechkarev, Denis; Mohs, Aaron M

2018-02-25

Self-assembled fluorescent nanomaterials based on small-molecule organic dyes are gaining increasing popularity in imaging and sensing applications over the past decade. This is primarily due to their ability to combine spectral property tunability and biocompatibility of small molecule organic fluorophores with brightness, chemical, and colloidal stability of inorganic materials. Such a unique combination of features comes with rich versatility of dye-based nanomaterials: from aggregates of small molecules to sophisticated core-shell nanoarchitectures involving hyperbranched polymers. Along with the ongoing discovery of new materials and better ways of their synthesis, it is very important to continue systematic studies of fundamental factors that regulate the key properties of fluorescent nanomaterials: their size, polydispersity, colloidal stability, chemical stability, absorption and emission maxima, biocompatibility, and interactions with biological interfaces. In this review, we focus on the systematic description of various types of organic fluorescent nanomaterials, approaches to their synthesis, and ways to optimize and control their characteristics. The discussion is built on examples from reports on recent advances in design and applications of such materials. Conclusions made from this analysis allow a perspective on future development of fluorescent nanomaterials design for biomedical and related applications. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Synthesis and evaluation of changes induced by solvent and substituent in electronic absorption spectra of some azo disperse dyes

NASA Astrophysics Data System (ADS)

Mohammadi, Asadollah; Yazdanbakhsh, Mohammad Reza; Farahnak, Lahya

2012-04-01

Five azo disperse dyes were prepared by diazotizing 4'-aminoacetophenone and p-anisidine and coupling with varies N-alkylated aromatic amines. Characterization of the dyes was carried out by using UV-vis, FTIR and 1H NMR spectroscopic techniques. The electronic absorption spectra of dyes are determined at room temperature in fifteen solvents with different polarities. The solvent dependent maximum absorption band shifts, were investigated using dielectric constant (ɛ), refractive index (n) and Kamlet-Taft polarity parameters (hydrogen bond donating ability (α), hydrogen bond accepting ability (β) and dipolarity/polarizability polarity scale (π*)). Acceptable agreement was found between the maximum absorption band of dyes and solvent polarity parameters especially with π*. The effect of substituents of coupler and/or diazo component on the color of dyes was investigated. The effects of acid and base on the visible absorption maxima of the dyes are also reported.

Precise identification and manipulation of adsorption geometry of donor-π-acceptor dye on nanocrystalline TiO₂ films for improved photovoltaics.

PubMed

Zhang, Fan; Ma, Wei; Jiao, Yang; Wang, Jingchuan; Shan, Xinyan; Li, Hui; Lu, Xinghua; Meng, Sheng

2014-12-24

Adsorption geometry of dye molecules on nanocrystalline TiO2 plays a central role in dye-sensitized solar cells, enabling effective sunlight absorption, fast electron injection, optimized interface band offsets, and stable photovoltaic performance. However, precise determination of dye binding geometry and proportion has been challenging due to complexity and sensitivity at interfaces. Here employing combined vibrational spectrometry and density functional calculations, we identify typical adsorption configurations of widely adopted cyanoacrylic donor-π bridge-acceptor dyes on nanocrystalline TiO2. Binding mode switching from bidentate bridging to hydrogen-bonded monodentate configuration with Ti-N bonding has been observed when dye-sensitizing solution becomes more basic. Raman and infrared spectroscopy measurements confirm this configuration switch and determine quantitatively the proportion of competing binding geometries, with vibration peaks assigned using density functional theory calculations. We further found that the proportion of dye-binding configurations can be manipulated by adjusting pH value of dye-sensitizing solutions. Controlling molecular adsorption density and configurations led to enhanced energy conversion efficiency from 2.4% to 6.1% for the fabricated dye-sensitized solar cells, providing a simple method to improve photovoltaic performance by suppressing unfavorable binding configurations in solar cell applications.

Can nitro groups really anchor onto TiO 2? Case study of dye-to-TiO 2 adsorption using azo dyes with NO 2 substituents

DOE PAGES

Zhang, Lei; Cole, Jacqueline M.

2016-06-21

The nitro group has recently been suggested as a new type of anchor for dye-sensitized solar cells (DSSCs) and has shown promising optoelectronic properties. Considering the excellent electron withdrawing ability of the nitro group and wider materials selection brought about by this substituent, it is helpful to evaluate the interfacial structures and photophysics of more organic dyes where NO 2 poses as the dye-to-TiO 2 anchor. A computational study on a family of azo dyes bearing a nitro group is presented in this paper, where the effect of certain side groups on their optical properties is examined. Both isolated dyemore » molecules and dye/TiO 2 nanocomposites are studied via density functional theory and time-dependent density functional theory, with complementary experimental UV/vis absorption spectroscopy and photovoltaic device testing. Results demonstrate that these nitro-containing dyes prefer a monodentate anchoring mode on a TiO 2 cluster. These nitro dyes reveal weak, but non-negligible, adsorption onto TiO 2; yet, very low photovoltaic performance once incorporated into a DSSC device. Finally, this poor delivery of nitro groups as DSSC anchors is ostensibly inconsistent with previous findings; but is rationalized via the “auxiliary anchor” concept.« less

Determining the exact number of dye molecules attached to colloidal CdSe/ZnS quantum dots in Förster resonant energy transfer assemblies

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

Kaiser, Uwe; Jimenez de Aberasturi, Dorleta; Vázquez-González, Margarita

2015-01-14

Semiconductor quantum dots functionalized with organic dye molecules are important tools for biological sensor applications. Energy transfer between the quantum dot and the attached dyes can be utilized for sensing. Though important, the determination of the real number of dye molecules attached per quantum dot is rather difficult. In this work, a method will be presented to determine the number of ATTO-590 dye molecules attached to CdSe/ZnS quantum dots based on time resolved spectral analysis. The energy transfer from the excited quantum dot to the attached ATTO-590 dye leads to a reduced lifetime of the quantum dot's excitons. The highermore » the concentration of dye molecules, the shorter the excitonic lifetime becomes. However, the number of dye molecules attached per quantum dot will vary. Therefore, for correctly explaining the decay of the luminescence upon photoexcitation of the quantum dot, it is necessary to take into account the distribution of the number of dyes attached per quantum dot. A Poisson distribution of the ATTO-590 dye molecules not only leads to excellent agreement between experimental and theoretical decay curves but also additionally yields the average number of dye molecules attached per quantum dot. In this way, the number of dyes per quantum dot can be conveniently determined.« less

Tuning the physical properties of organic sensitizers by replacing triphenylamine with new donors for dye sensitized solar cells - a theoretical approach.

PubMed

Ramkumar, Sekar; Manidurai, Paulraj

2017-02-15

New donor molecules with low ionization potential have been theoretically designed by replacing the benzene moieties in triphenylamine (TPA) with thiophene as well as furan. The designed new donors also exhibited planar structure, making an angle of 120° around the nitrogen atom that results in resonance effects through π-bonds of aryl rings. New sensitizers have been theoretically studied using DFT and TD-DFT by adopting these designed donors. UV-Vis absorption spectra, light harvesting ability (LHE) and electron injection ability (ΔG inject ) of the designed sensitizers have been calculated by taking L0 as reference. Orbital overlapping between donor and acceptor facilitates intra-molecular charge transfer, thereby increasing the interfacial electron injection from the sensitizer to the semiconductor nanoparticles. Our theoretical results demonstrate that sensitizers DTPA-AA and DFPA-AA have broader absorption and lower ΔG inject respectively compare to L0, this opens a new way for designing sensitizers for dye sensitized solar cells (DSSCs). All the dyes designed were found to be good light harvesters. Copyright © 2016 Elsevier B.V. All rights reserved.

Structural Heterogeneity and Quantitative FRET Efficiency Distributions of Polyprolines through a Hybrid Atomistic Simulation and Monte Carlo Approach

PubMed Central

Hoefling, Martin; Lima, Nicola; Haenni, Dominik; Seidel, Claus A. M.; Schuler, Benjamin; Grubmüller, Helmut

2011-01-01

Förster Resonance Energy Transfer (FRET) experiments probe molecular distances via distance dependent energy transfer from an excited donor dye to an acceptor dye. Single molecule experiments not only probe average distances, but also distance distributions or even fluctuations, and thus provide a powerful tool to study biomolecular structure and dynamics. However, the measured energy transfer efficiency depends not only on the distance between the dyes, but also on their mutual orientation, which is typically inaccessible to experiments. Thus, assumptions on the orientation distributions and averages are usually made, limiting the accuracy of the distance distributions extracted from FRET experiments. Here, we demonstrate that by combining single molecule FRET experiments with the mutual dye orientation statistics obtained from Molecular Dynamics (MD) simulations, improved estimates of distances and distributions are obtained. From the simulated time-dependent mutual orientations, FRET efficiencies are calculated and the full statistics of individual photon absorption, energy transfer, and photon emission events is obtained from subsequent Monte Carlo (MC) simulations of the FRET kinetics. All recorded emission events are collected to bursts from which efficiency distributions are calculated in close resemblance to the actual FRET experiment, taking shot noise fully into account. Using polyproline chains with attached Alexa 488 and Alexa 594 dyes as a test system, we demonstrate the feasibility of this approach by direct comparison to experimental data. We identified cis-isomers and different static local environments as sources of the experimentally observed heterogeneity. Reconstructions of distance distributions from experimental data at different levels of theory demonstrate how the respective underlying assumptions and approximations affect the obtained accuracy. Our results show that dye fluctuations obtained from MD simulations, combined with MC single photon kinetics, provide a versatile tool to improve the accuracy of distance distributions that can be extracted from measured single molecule FRET efficiencies. PMID:21629703

Investigating rhodamine B-labeled peptoids: scopes and limitations of its applications.

PubMed

Birtalan, Esther; Rudat, Birgit; Kölmel, Dominik K; Fritz, Daniel; Vollrath, Sidonie B L; Schepers, Ute; Bräse, Stefan

2011-01-01

The fluorophore rhodamine B is often used in biological assays. It is inexpensive, robust under a variety of reaction conditions, can be covalently linked to bioactive molecules, and has suitable spectral properties in terms of absorption and fluorescence wavelength. Nonetheless, there are some drawbacks: it can readily form a spirolactam compound, which is nonfluorescent, and therefore may not be the dye of choice for all fluorescence microscopy applications. Herein this spirolactam formation was observed by purifying such a labeled peptoid with high performance liquid chromatography (HPLC) and monitored in detail by making a series of analytical HPLC runs over time. Additionally, a small library of eight peptoids with rhodamine B as label was synthesized. Analysis of the absorption properties of these molecules demonstrated that the problem of fluorescence loss can be overcome by coupling secondary amines with rhodamine B.

The factors influencing nonlinear characteristics of the short-circuit current in dye-sensitized solar cells investigated by a numerical model.

PubMed

Shi, Yushuai; Dong, Xiandui

2013-06-24

A numerical model for interpretation of the light-intensity-dependent nonlinear characteristics of the short-circuit current in dye-sensitized solar cells is suggested. The model is based on the continuity equation and includes the influences of the nongeminate recombination between electrons and electron acceptors in the electrolyte and the geminate recombination between electrons and oxidized dye molecules. The influences of the order and rate constant of the nongeminate recombination reaction, the light-absorption coefficient of the dye, the film thickness, the rate constant of geminate recombination, and the regeneration rate constant on the nonlinear characteristics of the short-circuit current are simulated and analyzed. It is proposed that superlinear and sublinear characteristics of the short-circuit current should be attributed to low electron-collection efficiency and low dye-regeneration efficiency, respectively. These results allow a deep understanding of the origin of the nonlinear characteristics of the short-circuit current in solar cells. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermo-optical interactions in a dye-microcavity photon Bose-Einstein condensate

NASA Astrophysics Data System (ADS)

Alaeian, Hadiseh; Schedensack, Mira; Bartels, Clara; Peterseim, Daniel; Weitz, Martin

2017-11-01

Superfluidity and Bose-Einstein condensation are usually considered as two closely related phenomena. Indeed, in most macroscopic quantum systems, like liquid helium, ultracold atomic Bose gases, and exciton-polaritons, condensation and superfluidity occur in parallel. In photon Bose-Einstein condensates realized in the dye microcavity system, thermalization does not occur by direct interaction of the condensate particles as in the above described systems, i.e. photon-photon interactions, but by absorption and re-emission processes on the dye molecules, which act as a heat reservoir. Currently, there is no experimental evidence for superfluidity in the dye microcavity system, though effective photon interactions have been observed from thermo-optic effects in the dye medium. In this work, we theoretically investigate the implications of effective thermo-optic photon interactions, a temporally delayed and spatially non-local effect, on the photon condensate, and derive the resulting Bogoliubov excitation spectrum. The calculations suggest a linear photon dispersion at low momenta, fulfilling the Landau’s criterion of superfluidity. We envision that the temporally delayed and long-range nature of the thermo-optic photon interaction offer perspectives for novel quantum fluid phenomena.

Synthesis, optical and electrochemical properties of Zn-porphyrin for dye sensitized solar cell applications

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

Kotteswaran, S.; Pandian, M. Senthil; Ramasamy, P., E-mail: ramasamyp@ssn.edu.in

2016-05-23

Zn-Porphyrin dye has been synthesized by the reaction between aldehydes and pyrrole. The dye structure was confirmed by {sup 1}H NMR, {sup 13}C NMR spectrum. The functional group of the dye molecule was confirmed by FTIR spectrum. The UV-Vis-NIR absorption spectrum of Zn-Porphyrin in DMF solution was recorded in spectrophotometer. The UV-Vis NIR spectrum of dye exhibits a strong Soret band and Q-band. Cyclic Voltammograms were obtained with three electrode systems: Pt as counter electrode, saturated calomel used as a reference electrode and glassy carbon as working electrode at a scan rate of 100 mV/s. The curves recorded the oxidation ofmore » 0.5 mM compound Zn-Porphyrin in a dichloromethane solution containing 0.1M TBAP as supporting electrolyte, reveal two successive quasi reversible redox couples with the first anodic and cathodic peak potentials of -0.2 V and -1 V. The second anodic and cathodic peak potentials are 0.82 V and 0.01 V respectively.« less

Microscopic solvent structure of subcritical and supercritical methanol from ultraviolet/visible absorption and fluorescence spectroscopies

NASA Astrophysics Data System (ADS)

Bulgarevich, Dmitry S.; Sako, Takeshi; Sugeta, Tsutomu; Otake, Katsuto; Takebayashi, Yoshihiro; Kamizawa, Chiyoshi; Uesugi, Masayuki; Kato, Masahiro

1999-09-01

Ultraviolet/visible absorption and fluorescence spectroscopies at different temperatures and pressures were applied to investigate the microscopic solvent structures of subcritical and supercritical methanol using 4-nitroanisole, ethyl-(4-dimethylamino)benzoate, Reichardt's dye, and anthracene as the probe molecules. It was found that at temperatures higher than 150 °C the long winding chains of sequentially hydrogen-bonded methanol molecules were probably broken, but the small hydrogen-bonded aggregates possibly existed in methanol even at higher temperature. It was also found that the solvation process of the anthracene molecule in the S0-ground state obeyed the Langmuir adsorption model. However, in the case of fluorescence measurements in supercritical methanol, we detected deviations from the simple Langmuir adsorption model. These deviations were explained in terms of preferential solvation of the solvent molecules around photoexcited anthracene. Judging from the experimental results, it was concluded that the local density augmentation of the supercritical methanol around the nonpolar solute was a short-ranged effect, which did not correspond directly to the large isothermal compressibility of fluid near the critical point.

Ultrafast photoinduced dynamics of the 3,6-diaminoacridinium derivative ATTO 465 in solution.

PubMed

Arden-Jacob, Jutta; Drexhage, Karl-Heinz; Druzhinin, Sergey I; Ekimova, Maria; Flender, Oliver; Lenzer, Thomas; Oum, Kawon; Scholz, Mirko

2013-02-14

The excited state dynamics of the dye ATTO 465, a well-known fluorescence marker for biological applications, have been characterized in various solvents including THF, ethanol, methanol, water and the highly polar protic ionic liquid 2-hydroxyethylammonium formate (2-OH-EAF) by combining results from time-correlated single-photon counting (TCSPC) and ultrafast pump-supercontinuum probe (PSCP) spectroscopy as well as steady-state absorption and fluorescence. In water, 2-OH-EAF and two fluorinated alcohols, there is a pronounced blue-shift and broadening of the S(0) → S(1) absorption band and also a larger Stokes shift than in the other solvents, indicating a particular influence of hydrogen-bonding interactions. S(1) lifetimes from TCSPC at 25 °C range from 3.3 ns to 5.6 ns. An unusual increase in the S(1) lifetime with temperature is observed for ethanol and methanol, however water behaves in the opposite way. The behavior can be tentatively explained by a solvent- and temperature-dependent "proximity effect", where coupling of the close-lying S(1) and S(2) states influences the intramolecular relaxation rate of the dye. In addition, temperature-dependent complex equilibria of ATTO 465 with solvent molecules may influence the measured lifetimes. Several excited-state absorption (ESA) transitions are identified in the PSCP spectra, which are in good agreement with the position of the UV bands in the steady-state absorption spectra. Small shifts of the stimulated emission and ESA bands are consistent with solvation dynamics in the excited electronic state. An additional ~16 ps component in water, visible over the entire spectral range, is tentatively ascribed to a fast IC channel which is accessed by a fraction of ATTO 465 molecules.

Development of novel two-photon absorbing chromophores

NASA Astrophysics Data System (ADS)

Rogers, Joy E.; Slagle, Jonathan E.; McLean, Daniel G.; Sutherland, Richard L.; Krein, Douglas M.; Cooper, Thomas M.; Brant, Mark; Heinrichs, James; Kannan, Ramamurthi; Tan, Loon-Seng; Urbas, Augustine M.; Fleitz, Paul A.

2006-08-01

There has been much interest in the development of two-photon absorbing materials and many efforts to understand the nonlinear absorption properties of these dyes but this area is still not well understood. A computational model has been developed in our lab to understand the nanosecond nonlinear absorption properties that incorporate all of the measured one-photon photophysical parameters of a class of materials called AFX. We have investigated the nonlinear and photophysical properties of the AFX chromophores including the two-photon absorption cross-section, the excited state cross-section, the intersystem crossing quantum yield, and the singlet and triplet excited state lifetimes using a variety of experimental techniques that include UV-visible, fluorescence and phosphorescence spectroscopy, time correlated single photon counting, ultrafast transient absorption, and nanosecond laser flash photolysis. The model accurately predicts the nanosecond nonlinear transmittance data using experimentally measured parameters. Much of the strong nonlinear absorption has been shown to be due to excited state absorption from both the singlet and triplet excited states. Based on this understanding of the nonlinear absorption and the importance of singlet and triplet excited states we have begun to develop new two-photon absorbing molecules within the AFX class as well as linked to other classes of nonlinear absorbing molecules. This opens up the possibilities of new materials with unique and interesting properties. Specifically we have been working on a new class of two-photon absorbing molecules linked to platinum poly-ynes. In the platinum poly-yne chromophores the photophysics are more complicated and we have just started to understand what drives both the linear and non-linear photophysical properties.

Molecules for Fluorescence Detection of Specific Chemicals

NASA Technical Reports Server (NTRS)

Fedor, Steve

2008-01-01

A family of fluorescent dye molecules has been developed for use in on-off fluorescence detection of specific chemicals. By themselves, these molecules do not fluoresce. However, when exposed to certain chemical analytes in liquid or vapor forms, they do fluoresce (see figure). These compounds are amenable to fixation on or in a variety of substrates for use in fluorescence-based detection devices: they can be chemically modified to anchor them to porous or non-porous solid supports or can be incorporated into polymer films. Potential applications for these compounds include detection of chemical warfare agents, sensing of acidity or alkalinity, and fluorescent tagging of proteins in pharmaceutical research and development. These molecules could also be exploited for use as two-photon materials for photodynamic therapy in the treatment of certain cancers and other diseases. A molecule in this family consists of a fluorescent core (such as an anthracene or pyrene) attached to two end groups that, when the dye is excited by absorption of light, transfer an electron to the core, thereby quenching the fluorescence. The end groups can be engineered so that they react chemically with certain analytes. Upon reaction, electrons on the end groups are no longer available for transfer to the core and, consequently, the fluorescence from the core is no longer quenched. The chemoselectivity of these molecules can be changed by changing the end groups. For example, aniline end groups afford a capability for sensing acids or acid halides (including those contained in chemical warfare agents). Pyridine or bipyridyl end groups would enable sensing of metal ions. Other chemicals that can be selectively detected through suitable choice of end groups include glucose and proteins. Moreover, the fluorescent cores can be changed to alter light-absorption and -emission characteristics: anthracene cores fluoresce at wavelengths around 500 nm, whereas perylene cores absorb and emit at wavelengths of about 600 nm.

Dynamic perturbation effects upon the circular dichroism intensity induced in an aggregate of dye chromophores bound to biopolymers

NASA Astrophysics Data System (ADS)

Kamiya, Mamoru

1980-11-01

The dynamic perturbation effects of polarizable monomer perturbers upon the circular dichroism intensity arising from absorption transitions of an arbitrary aggregate of dye chromophores bound to a large host polymer are formulated using the linear response theory in the decorrelation approximation, where the interchromophoric retardation phase factors are eliminated by a first-order Taylor expansion which is compatible with the use of the retarded helix selection rules in the long-wavelength approximation. A space-averaged and closed-form formulation of the non-conservative circular dichroism intensity which is perturbed by intensity with the outside perturber transitions is derived in the limit of the weak dynamic perturbation where perturber—perturber interactions are negligible. The relevant formulation is applied in order to investigate the intercalation model dependence of the non-conservative circular dichroism intensity induced at the visible absorption band of proflavine molecules intercalated in either poly(A—T) or poly(G—C).

New Sm(III) complexes as electronic-excitation donors of the Seta-632 squaraine dye

NASA Astrophysics Data System (ADS)

Egorova, A. V.; Leonenko, I. I.; Aleksandrova, D. I.; Skripinets, Yu. V.; Antonovich, V. P.; Obukhova, E. N.; Patsenker, L. D.

2015-07-01

We have found optimal formation conditions of new Sm(III) chelate complexes with derivatives of oxoquinolinecarboxylic acid ( L 1 and L 2) and determined their spectral-luminescent characteristics (the luminescence and luminescence excitation wavelength maxima and the luminescence lifetimes). We have revealed that the Seta-632 squaraine dye (a fluorescent label of proteins and other biological molecules) quenches the luminescence of complexes Sm(III)- L 1 and Sm(III)- L 2. The quenching of chelate complexes is caused by the Förster resonant electronic-excitation energy transfer (FRET) from the donor (Sm(III)- L 1 or Sm(III)- L 2) to the acceptor (Seta-632). In this case, the luminescence intensity of the Seta-632 dye in the presence of Sm(III)- L 1 and Sm(III)- L 2 increases by factors of 64 and 27, respectively. The values of the Förster radii ( R 0(Sm- L1) = 38 Å, R 0(Sm- L2) = 35 Å) and the overlap integrals of the luminescence spectra of the two energy donors with the absorption spectrum of the acceptor ( J Sm- L1 = 1.22 × 1012 M-1 cm-1 nm4 and J Sm- L2 = 1.06 × 1012 M-1 cm-1 nm4), which have been calculated from the luminescence quantum intensity of the donors and from the absorption spectrum of the acceptor and its molar absorption coefficient, have made it possible to characterize the Seta-632 dye as an efficient quencher of the luminescence of Sm(III) ions. We are the first to propose Sm(III)- L 1 and Sm(III)- L 2 chelate complexes as FRET donors.

3D-QSPR Method of Computational Technique Applied on Red Reactive Dyes by Using CoMFA Strategy

PubMed Central

Mahmood, Uzma; Rashid, Sitara; Ali, S. Ishrat; Parveen, Rasheeda; Zaheer-ul-Haq; Ambreen, Nida; Khan, Khalid Mohammed; Perveen, Shahnaz; Voelter, Wolfgang

2011-01-01

Cellulose fiber is a tremendous natural resource that has broad application in various productions including the textile industry. The dyes, which are commonly used for cellulose printing, are “reactive dyes” because of their high wet fastness and brilliant colors. The interaction of various dyes with the cellulose fiber depends upon the physiochemical properties that are governed by specific features of the dye molecule. The binding pattern of the reactive dye with cellulose fiber is called the ligand-receptor concept. In the current study, the three dimensional quantitative structure property relationship (3D-QSPR) technique was applied to understand the red reactive dyes interactions with the cellulose by the Comparative Molecular Field Analysis (CoMFA) method. This method was successfully utilized to predict a reliable model. The predicted model gives satisfactory statistical results and in the light of these, it was further analyzed. Additionally, the graphical outcomes (contour maps) help us to understand the modification pattern and to correlate the structural changes with respect to the absorptivity. Furthermore, the final selected model has potential to assist in understanding the charachteristics of the external test set. The study could be helpful to design new reactive dyes with better affinity and selectivity for the cellulose fiber. PMID:22272108

A convenient method of attaching fluorescent dyes on single-walled carbon nanotubes pre-wrapped with DNA molecules.

PubMed

Tomura, Akihiro; Umemura, Kazuo

2018-04-15

We demonstrated the attachment of different kinds of dyes, Uranine, Rhodamime 800 (R800), and Indocyanine green (ICG), to single-walled carbon nanotubes pre-wrapped with single-stranded DNAs (ssDNA-SWCNTs). A new but simple method was employed, in which a dye solution was added to ssDNA-SWCNTs that had been prepared beforehand in the conventional way. Resulting conjugates of dyes, DNA, and SWCNTs were precisely evaluated by ultraviolet to near-infrared fluorescence/absorbance spectrometry and atomic force microscopy. In particular, simultaneous measurements of fluorescence and absorbance spectroscopy enabled us to find differences in the behaviors of the dyes on SWCNT surfaces. As a result, the fluorescence/absorbance spectra of dyes showed significant changes upon adsorption on SWCNTs. The fluorescence/absorbance peaks of Uranine, R800, and ICG were quenched by 41.3/2.8%, 72.3/48.9%, and 88.3/45.0%, respectively, in the presence of 11.5 μg/mL SWCNTs. We concluded firstly that by pre-wrapping SWCNTs with ssDNA, stable hybrids with these components were obtained even if the dyes used were relatively hydrophobic and secondly that Uranine retained light absorption on the surface of SWCNT while R800 and ICG did not. Copyright © 2018 Elsevier Inc. All rights reserved.

Slow and stored light by photo-isomerization induced transparency in dye doped chiral nematics.

PubMed

Wei, D; Bortolozzo, U; Huignard, J P; Residori, S

2013-08-26

Decelerating and stopping light is fundamental for optical processing, high performance sensor technologies and digital signal treatment, many of these applications relying on the ability of controlling the amplitude and phase of coherent light pulses. In this context, slow-light has been achieved by various methods, as coupling light into resonant media, Brillouin scattering in optical fibers, beam coupling in photorefractive and liquid crystal media or engineered dispersion in photonic crystals. Here, we present a different mechanism for slowing and storing light, which is based on photo-isomerization induced transparency of azo-dye molecules hosted in a chiral liquid crystal structure. Sharp spectral features of the medium absorption/dispersion, and the long population lifetime of the dye metastable state, enable the storage of light pulses with a significant retrieval after times much longer than the medium response time.

Co-sensitization of natural dyes for improved efficiency in dye-sensitized solar cell application

NASA Astrophysics Data System (ADS)

Kumar, K. Ashok; Subalakshmi, K.; Senthilselvan, J.

2016-05-01

In this paper, a new approach of co-sensitized DSSC based on natural dyes is investigated to explore the possible way to improve the power conversion efficiency. To realize this purpose 10 DSSC devices were fabricated using mono-sensitization and co-sensitization of ethanolic extracts of natural dye sensitizers obtained from Cactus fruit, Jambolana fruit, Curcumin and Bermuda grass. The optical absorption spectrum of the mono and hybrid dye extracts were studied by UV-Visible absorption spectrum. It shows the characteristic absorption peaks in visible region corresponds to the presence of natural pigments of anthocyanin, betacyanin and chlorophylls. Absorption spectrum of hybrid dyes reveals a wide absorption band in visible region with improved extinction co-efficient and it is favorable for increased light harvesting nature. The power conversion efficiency of DSSC devices were calculated using J-V curve and the maximum efficiency achieved in the present work is noted to be ~0.61% for Cactus-Bermuda co-sensitized DSSC.

Laser optogalvanic spectroscopy of molecules

NASA Technical Reports Server (NTRS)

Webster, C. R.; Rettner, C. T.

1983-01-01

In laser optogalvanic (LOG) spectroscopy, a tunable laser is used to probe the spectral characteristics of atomic or molecular species within an electrical discharge in a low pressure gas. Optogalvanic signals arise when the impedance of the discharge changes in response to the absorption of laser radiation. The technique may, therefore, be referred to as impedance spectroscopy. This change in impedance may be monitored as a change in the voltage across the discharge tube. LOG spectra are recorded by scanning the wavelength of a chopped CW dye laser while monitoring the discharge voltage with a lock-in amplifier. LOG signals are obtained if the laser wavelength matches a transition in a species present in the discharge (or flame), and if the absorption of energy in the laser beam alters the impedance of the discharge. Infrared LOG spectroscopy of molecules has been demonstrated and may prove to be the most productive application in the field of optogalvanic techniques.

Sub-wavelength plasmon laser

DOEpatents

Bora, Mihail; Bond, Tiziana C.

2016-04-19

A plasmonic laser device has resonant nanocavities filled with a gain medium containing an organic dye. The resonant plasmon frequencies of the nanocavities are tuned to align with both the absorption and emission spectra of the dye. Variables in the system include the nature of the dye and the wavelength of its absorption and emission, the wavelength of the pumping radiation, and the resonance frequencies of the nanocavities. In addition the pumping frequency of the dye is selected to be close to the absorption maximum.

Effect of electron withdrawing unit for dye-sensitized solar cell based on D-A-π-A organic dyes

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

Kwon, Dong Yuel; Chang, Dong Min; Kim, Young Sik, E-mail: youngkim@hongik.ac.kr

2014-10-15

Highlights: • To gain the red-shifted absorption spectra, withdrawing unit was substituted in dye. • By the introduction of additional withdrawing unit, LUMOs level of dye are decreased. • Decreasing LUMOs level of dye caused the red-shifted absorption spectra of dye. • Novel acceptor, DCRD, showed better photovoltaic properties than cyanoacetic acid. - Abstract: In this work, two novel D-A-π-A dye sensitizers with triarylamine as an electron donor, isoindigo and cyano group as electron withdrawing units and cyanoacetic acid and 2-(1,1-dicyanomethylene) rhodanine as an electron acceptor for an anchoring group (TICC, TICR) were designed and investigated with the ID6 dyemore » as the reference. The difference in HOMO and LUMO levels were compared according to the presence or absence of isoindigo in ID6 (TC and ID6). To gain insight into the factors responsible for photovoltaic performance, we used density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. Owing to different LUMO levels for each acceptor, the absorption band and molar extinction coefficient of each dye was different. Among the dyes, TICR showed more red-shifted and broader absorption spectra than other dyes and had a higher molar extinction coefficient than the reference. It is expected that TICR would show better photovoltaic properties than the other dyes, including the reference dye.« less

pH-sensitive optrode

DOEpatents

Hirschfeld, Tomas B.; Wang, Francis T.

1989-01-01

An apparatus is provided for remotely monitoring pH. A support material is provided on which organic dye molecules are covalently attached at a surface density falling within a predetermined range. The pH dependent fluorescence response of the bound organic dye molecules depends critically on surface density of the organic dye molecules bound to the support material and the nature of the covalent linkage betwen the organic dye molecules and the support material. The invention is operated by contacting the support material on which the organic dye is attached with the fluid whose pH is to be determined. When in contact, the organic dye on the support material is illuminated so that it is caused to fluoresce. The intensity of organic dye fluorescence is then related to pH.

Coumarin-BODIPY hybrids by heteroatom linkage: versatile, tunable and photostable dye lasers for UV irradiation.

PubMed

Esnal, I; Duran-Sampedro, G; Agarrabeitia, A R; Bañuelos, J; García-Moreno, I; Macías, M A; Peña-Cabrera, E; López-Arbeloa, I; de la Moya, S; Ortiz, M J

2015-03-28

Linking amino and hydroxycoumarins to BODIPYs through the amino or hydroxyl group lets the easy construction of unprecedented photostable coumarin-BODIPY hybrids with broadened and enhanced absorption in the UV spectral region, and outstanding wavelength-tunable laser action within the green-to-red spectral region (∼520-680 nm). These laser dyes allow the generation of a valuable tunable UV (∼260-350 nm) laser source by frequency doubling, which is essential to study accurately the photochemistry of biological molecules under solar irradiation. The tunability is achieved by selecting the substitution pattern of the hybrid. Key factors are the linking heteroatom (nitrogen vs. oxygen), the number of coumarin units joined to the BODIPY framework and the involved linking positions.

Ab-initio and DFT methodologies for computing hyperpolarizabilities and susceptibilities of highly conjugated organic compounds for nonlinear optical applications

NASA Astrophysics Data System (ADS)

Karakas, A.; Karakaya, M.; Ceylan, Y.; El Kouari, Y.; Taboukhat, S.; Boughaleb, Y.; Sofiani, Z.

2016-06-01

In this talk, after a short introduction on the methodologies used for computing dipole polarizability (α), second and third-order hyperpolarizability and susceptibility; the results of theoretical studies performed on density functional theory (DFT) and ab-initio quantum mechanical calculations of nonlinear optical (NLO) properties for a few selected organic compounds and polymers will be explained. The electric dipole moments (μ) and dispersion-free first hyperpolarizabilities (β) for a family of azo-azulenes and a styrylquinolinium dye have been determined by DFT at B3LYP level. To reveal the frequency-dependent NLO behavior, the dynamic α, second hyperpolarizabilities (γ), second (χ(2)) and third-order (χ(3)) susceptibilites have been evaluated using time-dependent HartreeFock (TDHF) procedure. To provide an insight into the third-order NLO phenomena of a series of pyrrolo-tetrathiafulvalene-based molecules and pushpull azobenzene polymers, two-photon absorption (TPA) characterizations have been also investigated by means of TDHF. All computed results of the examined compounds are compared with their previous experimental findings and the measured data for similar structures in the literature. The one-photon absorption (OPA) characterizations of the title molecules have been theoretically obtained by configuration interaction (CI) method. The highest occupied molecular orbitals (HOMO), the lowest unoccupied molecular orbitals (LUMO) and the HOMO-LUMO band gaps have been revealed by DFT at B3LYP level for azo-azulenes, styrylquinolinium dye, push-pull azobenzene polymers and by parametrization method 6 (PM6) for pyrrolo-tetrathiafulvalene-based molecules.

Synthesis, characterization, and spectroscopic investigation of benzoxazole conjugated Schiff bases.

PubMed

Santos, Fabiano S; Costa, Tania M H; Stefani, Valter; Gonçalves, Paulo F B; Descalzo, Rodrigo R; Benvenutti, Edilson V; Rodembusch, Fabiano S

2011-11-24

Two Schiff bases were synthesized by reaction of 2-(4'-aminophenyl)benzoxazole derivatives with 4-N,N-diethylaminobenzaldehyde. UV-visible (UV-vis) and steady-state fluorescence in solution were applied in order to characterize its photophysical behavior. The Schiff bases present absorption in the UV region with fluorescence emission in the blue-green region, with a large Stokes' shift. The UV-vis data indicates that each dye behaves as two different chromophores in solution in the ground state. The fluorescence emission spectra of the dye 5a show that an intramolecular proton transfer (ESIPT) mechanism takes place in the excited state, whereas a twisted internal charge transfer (TICT) state is observed for the dye 5b. Theoretical calculations were performed in order to study the conformation and polarity of the molecules at their ground and excited electronic states. Using density functional theory (DFT) methods at theoretical levels BLYP/Aug-SV(P) for geometry optimizations and B3LYP/6-311++G(2d,p) for single-point energy evaluations, the calculations indicate that the lowest energy conformations are in all cases nonplanar and that the dipole moments of the excited state relaxed structures are much larger than those of the ground state structures, which corroborates the experimental UV-vis absorption results.

Femtosecond Laser Fabricated Ag@Au and Cu@Au Alloy Nanoparticles for Surface Enhaned Raman Spectrosocpy Based Trace Explosives Detection

NASA Astrophysics Data System (ADS)

Sree Satya Bharati, Moram; Byram, Chandu; Soma, Venugopal R.

2018-03-01

Herein we present results from our detailed studies on the fabrication of Ag@Au and Cu@Au alloy nanoparticles (NPs) using the femtosecond laser ablation in liquid technique. The NPs were obtained by ablating the pure Ag, Cu targets (bulk) in HAuCl4 (5 mM) solution. The absorption properties of the obtained NPs colloids were characterized using UV-Visible absorption spectrometer and their size, shape, and crystallinity were investigated using the XRD, FESEM and TEM techniques. The fabricated NPs were utilized for sensing of explosive molecules such as 2, 4, 6-trinitrophenol (PA), 2, 4-dinitrotoluene (DNT) and a common dye methylene blue (MB) using the surface enhanced Raman spectroscopy (SERS) technique. The detection limit in terms of weight was as low as few nano-grams in the case of nitroaromatic explosive compounds (PA, DNT) and few picograms in the case of a common dye molecule (MB). Typical enhancement factors achieved were estimated to be 104, 105 and 107, respectively, for PA, DNT, and MB. The significance of the present work lies in exploring the performance of the prepared NPs being used as SERS substrates for explosives detection using a portable Raman instrument. Such capability enables one to carry the spectrometer to the point of interest in the field and evaluate any hazardous samples within a short period of time.

Molecular design of donor-acceptor dyes for efficient dye-sensitized solar cells I: a DFT study.

PubMed

El-Shishtawy, Reda M; Asiri, Abdullah M; Aziz, Saadullah G; Elroby, Shaaban A K

2014-06-01

Dye-sensitized solar cells (DSSCs) have drawn great attention as low cost and high performance alternatives to conventional photovoltaic devices. The molecular design presented in this work is based on the use of pyran type dyes as donor based on frontier molecular orbitals (FMO) and theoretical UV-visible spectra in combination with squaraine type dyes as an acceptor. Density functional theory has been used to investigate several derivatives of pyran type dyes for a better dye design based on optimization of absorption, regeneration, and recombination processes in gas phase. The frontier molecular orbital (FMO) of the HOMO and LUMO energy levels plays an important role in the efficiency of DSSCs. These energies contribute to the generation of exciton, charge transfer, dissociation and exciton recombination. The computations of the geometries and electronic structures for the predicted dyes were performed using the B3LYP/6-31+G** level of theory. The FMO energies (EHOMO, ELUMO) of the studied dyes are calculated and analyzed in the terms of the UV-visible absorption spectra, which have been examined using time-dependent density functional theory (TD-DFT) techniques. This study examined absorption properties of pyran based on theoretical UV-visible absorption spectra, with comparisons between TD-DFT using B3LYP, PBE, and TPSSH functionals with 6-31+G (d) and 6-311++G** basis sets. The results provide a valuable guide for the design of donor-acceptor (D-A) dyes with high molar absorptivity and current conversion in DSSCs. The theoretical results indicated 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran dye (D2-Me) can be effectively used as a donor dye for DSSCs. This dye has a low energy gap by itself and a high energy gap with squaraine acceptor type dye, the design that reduces the recombination and improves the photocurrent generation in solar cell.

pH-sensitive optrode

DOEpatents

Hirschfeld, T.B.; Wang, F.T.

1989-02-07

An apparatus is provided for remotely monitoring pH. A support material is provided on which organic dye molecules are covalently attached at a surface density falling within a predetermined range. The pH dependent fluorescence response of the bound organic dye molecules depends critically on surface density of the organic dye molecules bound to the support material and the nature of the covalent linkage between the organic dye molecules and the support material. The invention is operated by contacting the support material on which the organic dye is attached with the fluid whose pH is to be determined. When in contact, the organic dye on the support material is illuminated so that it is caused to fluoresce. The intensity of organic dye fluorescence is then related to pH. 4 figs.

Studies of absorption coefficient cum electro-optic performance of polymer dispersed liquid crystal doped with CNT and dichroic dye

NASA Astrophysics Data System (ADS)

Sharma, Vandna; Kumar, Pankaj

2017-11-01

Absorption coefficient of doped polymer dispersed liquid crystals (PDLCs) is a critical factor for their device performance and depends on dopants parameters like solubility, order parameter and extinction coefficients, in addition to configuration and orientation of the droplets. In this study, a fixed amount (0.125% wt/wt) of multiwall carbon nanotubes (CNTs) and orange azo dichroic dye was doped in PDLC and measured the OFF state absorption coefficient. Considering the theory based on Beer's law and followed by extinction coefficients of CNT and dye, the OFF state transmission for dye doped PDLC was found lower compared to CNT doped PDLC. As a result, absorption coefficient for dye doped PDLC was higher and resulted in the superior contrast ratio. The experimental results were found be consistent with the theoretical results.

Aqueous solvation from the water perspective.

PubMed

Ahmed, Saima; Pasti, Andrea; Fernández-Terán, Ricardo J; Ciardi, Gustavo; Shalit, Andrey; Hamm, Peter

2018-06-21

The response of water re-solvating a charge-transfer dye (deprotonated Coumarin 343) after photoexcitation has been measured by means of transient THz spectroscopy. Two steps of increasing THz absorption are observed, a first ∼10 ps step on the time scale of Debye relaxation of bulk water and a much slower step on a 3.9 ns time scale, the latter of which reflecting heating of the bulk solution upon electronic relaxation of the dye molecules from the S 1 back into the S 0 state. As an additional reference experiment, the hydroxyl vibration of water has been excited directly by a short IR pulse, establishing that the THz signal measures an elevated temperature within ∼1 ps. This result shows that the first step upon dye excitation (10 ps) is not limited by the response time of the THz signal; it rather reflects the reorientation of water molecules in the solvation layer. The apparent discrepancy between the relatively slow reorientation time and the general notion that water is among the fastest solvents with a solvation time in the sub-picosecond regime is discussed. Furthermore, non-equilibrium molecular dynamics simulations have been performed, revealing a close-to-quantitative agreement with experiment, which allows one to disentangle the contribution of heating to the overall THz response from that of water orientation.

Determination of the orientation of fluorescent labels relative to myosin S1 in solution from time-resolved fluorescence anisotropy experiments

NASA Astrophysics Data System (ADS)

van der Heide, Uulke A.; Gerritsen, Hans C.; Trayer, Ian P.; Levine, Yehudi K.

1992-04-01

The time-resolved fluorescence anisotropy of myosin S1 covalently labeled with Eosin-5- maleimide and 1,5-I-AEDANS was measured in solution. Each probe was specifically attached at one SH-group on the S1. The two most reactive SH sites on the heavy chain of the myosin S1 were used. The fluorescence anisotropy was measured at different excitation wavelengths. In this way, several absorption moments were utilized, each having a distinct orientation in the frame of the dye. The orientations of the transition moments in the dyes were determined in a separate experiment using an angle resolved fluorescence depolarization experiment on dyes embedded in stretched matrices of PVA polymers. The anisotropy decay curves exhibit fast (<3 ns) and slow (> 100 ns) components. The slow decay components reflect the motion of the large protein molecules. The fast anisotropy decay are attributed to a fast, but restricted, motion of the bound dye relative to the protein as experiments on free dyes in solution reveal subnanosecond anisotropy decays. The anisotropy decays have been analyzed in terms of a model which describes the restricted motion of the dye molecule relative to the protein and the overall rotation of the dye-protein complex in solution. An important element in the model is the incorporation of the orientational distribution of the dye relative to the protein. The observed anisotropy decays were analyzed using a global target approach in which the experimental data obtained at different excitation wavelengths are fitted simultaneously to the theoretical model. It is important to note that the orientational distribution of the dye relative to the protein, as well as the rotational correlation times of the motions for a dye attached to a given binding site, are independent of the excitation wavelength used. This leads to a reduction in the number of independent parameters optimized by the nonlinear least squares procedure. The orientational distribution of the dye relative to the protein obtained in this way is particularly useful for the interpretation of fluorescence depolarization data obtained from labeled muscle fibers. Indeed, knowledge of the distribution function of a dye attached to a binding site of the S1 protein is a prerequisite for a probe-independent determination of the orientational distribution of the S1 proteins themselves in the muscle fiber.

Magnetic Fe3O4@V2O5/rGO nanocomposite as a recyclable photocatalyst for dye molecules degradation under direct sunlight irradiation.

PubMed

Boruah, Purna K; Szunerits, Sabine; Boukherroub, Rabah; Das, Manash R

2018-01-01

Reduced graphene oxide nanosheets decorated with Fe 3 O 4 and V 2 O 5 nanoparticles as a magnetically recoverable nanocomposite (Fe 3 O 4 @V 2 O 5 /rGO) was synthesized by a simple solution chemistry approach. The synthesized nanocomposite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometer (VSM), Fourier transform infrared (FTIR), fluorescence, and zeta potential measurements. The narrow band gap and different band gap energies of Fe 3 O 4 and V 2 O 5 proved to be suitable for the absorption of visible light in the solar spectrum. The Fe 3 O 4 @V 2 O 5 /rGO displayed indeed excellent photocatalytic activity towards the degradation of harmful cationic Bismarck Brown (BB) as well as anionic Acid Orange 7 (AO) dyes under direct sunlight irradiation. The photocatalytic activity of the Fe 3 O 4 @V 2 O 5 /rGO is influenced by solution pH, catalyst loading, initial dye concentration and the presence of different inorganic ions (NH 4 + , Na + , Mg 2+ , Ca 2+, SO 4 2- , Br - , NO 3 - , Cl - , HCO 3 - ). This study provides a new scientific knowledge on the sunlight driven photocatalytic degradation of dye molecules using novel mixed metal oxide/rGO nanocomposite photocatalyst. Copyright © 2017 Elsevier Ltd. All rights reserved.

Composite fluorescent nanoparticles for biomedical imaging.

PubMed

Pansare, Vikram J; Bruzek, Matthew J; Adamson, Douglas H; Anthony, John; Prud'homme, Robert K

2014-04-01

In the rapidly expanding field of biomedical imaging, there is a need for nontoxic, photostable, and nonquenching fluorophores for fluorescent imaging. We have successfully encapsulated a new, extremely hydrophobic, pentacene-based fluorescent dye within polymeric nanoparticles (NPs) or nanocarriers (NCs) via the Flash NanoPrecipitation (FNP) process. Nanoparticles and dye-loaded micelles were formulated by FNP and characterized by dynamic light scattering, fluorescence spectroscopy, UV-VIS absorbance spectroscopy, and confocal microscopy. These fluorescent particles were loaded from less than 1% to 78% by weight core loading and the fluorescence maximum was found to be at 2.3 wt.%. The particles were also stably formed at 2.3% core loading from 20 up to 250 nm in diameter with per-particle fluorescence scaling linearly with the NC core volume. The major absorption peaks are at 458, 575, and 625 nm, and the major emission peaks at 635 and 695 nm. In solution, the Et-TP5 dye displays a strong concentration-dependent ratio of the emission intensities of the first two emission peaks, whereas in the nanoparticle core the spectrum is independent of concentration over the entire concentration range. A model of the fluorescence quenching was consistent with Förster resonant energy transfer as the cause of the quenching observed for Et-TP5. The Förster radius calculated from the absorption and emission spectra of Et-TP5 is 4.1 nm, whereas the average dye spacing in the particles at the maximum fluorescence is 3.9 nm. We have successfully encapsulated Et-TP5, a pentacene derivative dye previously only used in light-emitting diode applications, within NCs via the FNP process. The extreme hydrophobicity of the dye keeps it encapsulated in the NC core, its extended pentacene structure gives it relatively long wavelength emission at 695 nm, and the pentacene structure, without oxygen or nitrogen atoms in its core, makes it highly resistant to photobleaching. Its bulky side groups minimize self-quenching and localization within the nanoparticle core prevents interaction of the dye with biological surfaces, or molecules in diagnostic assays. Loading of dye in the NP core allows 25 times more dye to be delivered than if it were conjugated onto the nanocarrier surface. The utility of the dye for quantifying nanoparticle binding is demonstrated. Studies to extend the wavelength range of these pentacene dyes into the near infra-red are underway.

Feasibility study on the use of liquid crystal/dye cells for digital signage

NASA Astrophysics Data System (ADS)

Itaya, Shunsuke; Azumi, Nada Dianah B. M.; Ohta, Masamichi; Ozawa, Shintaro; Fujieda, Ichiro

2016-03-01

Elongated dye molecules orient themselves with surrounding liquid crystal molecules. We propose to incorporate such a guest-host cell in a screen of a projection display. This configuration might be applied for digital signage to be installed on building walls. Dual-mode operation is realized by the bias applied to the cell. In display-mode, the dye molecules are oriented in parallel to the substrate of the cell. When excited by ultra-violet light, photoluminescence (PL) is generated. Because it is mostly perpendicular to the long axis of the molecule, it exits the cell efficiently. In powerharvesting mode, they are oriented vertically. The PL generated by ambient light is directed to edge surfaces where solar cells are mounted. In experiment, we fabricated a cell with commonly-available materials (coumarin 6 and a nematic liquid crystal). Anti-parallel alignment condition was adopted. We recorded PL spectra from the cell for the two excitation conditions. First, the center of the cell was irradiated by a 1.69mW blue laser beam. Second, the whole cell was uniformly exposed to the light from a fluorescent lamp at illuminance of 800lx. From the measured spectra for these cases, the contrast of luminance is calculated to be 3.2 ×105 . This factor is improved to 5 7.5×105 by attaching a polarizer sheet on the cell surface. The optical power reaching its edge surfaces is measured and it roughly agrees with the prediction by a simple model neglecting self-absorption. Development of phosphor materials with a large Stokes shift is desired to boost performance of the proposed system.

Asymmetrical squaraines for high-performance small-molecule organic solar cells with a short circuit current of over 12 mA cm(-2).

PubMed

Chen, Yao; Zhu, Youqin; Yang, Daobin; Luo, Qian; Yang, Lin; Huang, Yan; Zhao, Suling; Lu, Zhiyun

2015-04-11

An asymmetrical squaraine dye (Py-3) with its two electron-donating aryl groups directly linked to the electron-withdrawing squaric acid core possesses an ideal bandgap of 1.33 eV, together with an intense and broad absorption band in the range 550-950 nm. Hence, the resulting solution-processed solar cells display an impressive Jsc of 12.03 mA cm(-2) and a PCE of 4.35%.

Metal oxide-encapsulated dye-sensitized photoanodes for dye-sensitized solar cells

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

Hupp, Joseph T.; Son, Ho-Jin

2016-01-12

Dye-sensitized semiconducting metal oxide films for photoanodes, photoanodes incorporating the films and DSCs incorporating the photoanodes are provided. Also provided are methods for making the dye sensitized semiconducting metal oxide films. The methods of making the films are based on the deposition of an encapsulating layer of a semiconducting metal oxide around the molecular anchoring groups of photosensitizing dye molecules adsorbed to a porous film of the semiconducting metal oxide. The encapsulating layer of semiconducting metal oxide is formed in such a way that it is not coated over the chromophores of the adsorbed dye molecules and, therefore, allows themore » dye molecules to remain electrochemically addressable.« less

Nitrogen doped nanocrystalline semiconductor metal oxide: An efficient UV active photocatalyst for the oxidation of an organic dye using slurry Photoreactor.

PubMed

Ramachandran, Saranya; Sivasamy, A; Kumar, B Dinesh

2016-12-01

Water pollution is a cause for serious concern in today's world. A major contributor to water pollution is industrial effluents containing dyes and other organic molecules. Waste water treatment has become a priority area in today's applied scientific research as it seeks to minimize the toxicity of the effluents being discharged and increase the possibility of water recycling. An efficient and eco-friendly way of degrading toxic molecules is to use nano metal-oxide photocatalysts. The present study aims at enhancing the photocatalytic activity of a semiconductor metal oxide by doping it with nitrogen. A sol-gel cum combustion method was employed to synthesize the catalyst. The prepared catalyst was characterized by FT-IR, XRD, UV-DRS, FESEM and AFM techniques. UV-DRS result showed the catalyst to possess band gap energy of 2.97eV, thus making it active in the UV region of the spectrum. Its photocatalytic activity was evaluated by the degradation of a model pollutant-Orange G dye, under UV light irradiation. Preliminary experiments were carried out to study the effects of pH, catalyst dosage and initial dye concentration on the extent of dye degradation. Kinetic studies revealed that the reaction followed pseudo first order kinetics. The effect of electrolytes on catalyst efficiency was also studied. The progress of the reaction was monitored by absorption studies and measuring the reduction in COD. The catalyst thus prepared was seen to have a high photocatalytic efficiency. The use of this catalyst is a promising means of waste water treatment. Copyright © 2016 Elsevier Inc. All rights reserved.

Tunable random lasing behavior in plasmonic nanostructures

NASA Astrophysics Data System (ADS)

Yadav, Ashish; Zhong, Liubiao; Sun, Jun; Jiang, Lin; Cheng, Gary J.; Chi, Lifeng

2017-01-01

Random lasing is desired in plasmonics nanostructures through surface plasmon amplification. In this study, tunable random lasing behavior was observed in dye molecules attached with Au nanorods (NRs), Au nanoparticles (NPs) and Au@Ag nanorods (NRs) respectively. Our experimental investigations showed that all nanostructures i.e., Au@AgNRs, AuNRs & AuNPs have intensive tunable spectral effects. The random lasing has been observed at excitation wavelength 532 nm and varying pump powers. The best random lasing properties were noticed in Au@AgNRs structure, which exhibits broad absorption spectrum, sufficiently overlapping with that of dye Rhodamine B (RhB). Au@AgNRs significantly enhance the tunable spectral behavior through localized electromagnetic field and scattering. The random lasing in Au@AgNRs provides an efficient coherent feedback for random lasers.

Solvent effects on the photophysical properties of coumarin dye

NASA Astrophysics Data System (ADS)

Bhavya, P.; Melavanki, Raveendra; Manjunatha, M. N.; Koppal, Varsha; Patil, N. R.; Muttannavar, V. T.

2018-05-01

The absorption and emission spectrum of fluorescent coumarin dye namely, 3-Hydroxy-3-[2-oxo-2-(3-oxo-3H-benzo[f]chromen-2-yl)-ethyl]-1,3-dihydro-indol-2-one [3HBCD] has been recorded at room temperature in solvents of different polarities. The exited state dipole moments (μe) were estimated from Lippert's, Bakhshiev's and Kawski-Chamma-Viallet's equations using the variation of Stoke's shift with the solvent dielectric constant and refractive index. The geometry of the molecule was fully optimized and the μg was also calculated theoretically by Gaussian 03 software using B3LYP/6-31g* level of theory. The μg and μg were calculated by means of solvatochromic shift method. It was observed that μe was higher than μg, indicating a substantial redistribution of the π-electron densities in a more polar excited state for the selected coumarin dye. Further, the changes in the dipole moment (Δμ) was calculated from solvatochromic shift method.

Photophysical properties of fluorescently-labeled peptoids.

PubMed

Rudat, Birgit; Birtalan, Esther; Vollrath, Sidonie B L; Fritz, Daniel; Kölmel, Dominik K; Nieger, Martin; Schepers, Ute; Müllen, Klaus; Eisler, Hans-Jürgen; Lemmer, Uli; Bräse, Stefan

2011-09-01

Fluorescently-labeled biomolecules are often utilized in biochemical or cellular experiments without further detailed spectroscopical characterization. This report is intended to narrow this gap and therefore presents the photophysical investigation of a library of 17 fluorescently-labeled molecules, namely peptoid transporters. First, one peptoid structure is labeled with seven different fluorophores and the spectroscopical properties are examined. Absorption and fluorescence maxima are almost identical for free dyes and conjugated dyes, suggesting free choice of a spectrally suitable fluorophore for different applications. Otherwise, extinction coefficients and quantum yields, and therefore the brightness of all seven dyes are strongly influenced. For the fluorophores, e.g. rhodamine B, the extent of this influence depends on the peptoid itself. This is shown by comparing different structures in the second part of this report. Especially the side chain functionalities influence the brightness. And finally, peptoids having two identical fluorescent labels are presented, which show decreased quantum yields. Possible reasons for the observed photophysical properties are discussed. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

Theoretical study of the design dye-sensitivity for usage in the solar cell device

NASA Astrophysics Data System (ADS)

Alrikabi, Alaa

There are many applications in the polymer chemistry, pharmaceutical, agricultural and industrial fields of the thiadiazole molecule and their derivatives. Allowance of the energy gap of the polymer conjugated is an object of great interesting debit for the possible removal of a doping in the preparation of highly conductivity polymers. Thiadiazoles derivatives are structural foundation of the polymer materials. In this present work, the electronic properties of graphene nanoflakes (GNFs)-phenanthrene-1,3,4-thiadiazoles oligomers are studied and discussed. Where thiadiazoles is expanded from one to 9 unit's molecules at the structure. The energy gap, HOMO, LUMO distribution, total energy, Fermi level energy, work function, maximum wavelength absorption, vertical absorption energies, and oscillator strengths are calculated for each molecule. All calculations are carry out by usage density function theory (DFT) and depended time density function theory (TD-DFT) with the B3LYP/6-31G model in the Gaussian 09W software packages. Results show that increasing the number of monomeric units lead to great enhance in the electronic properties, which caused it decreased the band gap from 3.17 eV in the system with one unit of thiadiazole just to 1.35 eV in the system with 9 units of thiadiazole. This case is raised the value of maximum absorption wavelengths to >500 nm to give the better performance in optoelectronic and solar cell, as these structures have prime absorption bands within the solar spectrum.

Enhancing the power conversion efficiency of dye-sensitized solar cells via molecular plasmon-like excitations.

PubMed

Li, Jian-Hao; Gryn'ova, Ganna; Prlj, Antonio; Corminboeuf, Clémence

2017-02-21

We introduce a tactic for employing molecular plasmon-like excitations to enhance solar-to-electric power conversion efficiency of dye-sensitized solar cells. We offer general design principles of dimeric dyes, in which a strong plasmonic interaction between two π-conjugated moieties is promoted. The π-stacked conformations of these dimeric dyes result in a desirable broadened absorption and a longer absorption onset wavelength.

Sonocatalytic degradation of malachite green oxalate by a semiconductor metal oxide nanocatalyst.

PubMed

Bhavani, R; Sivasamy, A

2016-12-01

Advanced Oxidation Process (AOP) technologies are considered to be better technique for the degradation or mineralization of many recalcitrant compounds and pollutants. In the present study heterogeneous sonocatalytic degradation of a model organic compound such as Malachite green oxalate (MGO) was carried out in the aqueous phase. Zinc oxide nanorods were prepared by precipitation method employing zinc acetates as precursors and were characterized by FT-IR, XRD, FE-SEM and EDAX analysis. Degradation of MGO in the aqueous phase was studied in detail under the sonocatalytic process. Effects of pH, dye concentration, oxidant concentration, kinetics and effect of electrolytes on dye degradation were carried out to check the efficiency of the sonocatalyst. Effect of energy input on the degradation processes was also investigated. The degradation of dye molecules were monitored by UV-visible spectrophotometer and Chemical Oxygen demand (COD). The dye molecules were readily degraded at above 90% in the pH range 5.0-7.0 under ultrasound with zinc oxide nanorods. The interference of electrolytes like NaCl, KCl, Na 2 CO 3 , NaHCO 3 and MgSO 4 on the degradation of dye molecules were also studied on the sonocatalytic degradation of MGO. From the kinetic studies it was observed that at lower initial concentration of dye molecules the degradation efficiency was above 90%. The rate of the reaction decreased on increasing the initial dye concentrations of the dye molecules. It was observed that the complete mineralization of dye molecules was achieved without the formation of toxic by-products. The reusability of the catalyst also showed the effective degradation of the dye molecules up to five cycles without loss of the catalytic activities. Copyright © 2015 Elsevier Inc. All rights reserved.

Third-order nonlinear optical properties of organic azo dyes by using strength of nonlinearity parameter and Z-scan technique

NASA Astrophysics Data System (ADS)

Motiei, H.; Jafari, A.; Naderali, R.

2017-02-01

In this paper, two chemically synthesized organic azo dyes, 2-(2,5-Dichloro-phenyazo)-5,5-dimethyl-cyclohexane-1,3-dione (azo dye (i)) and 5,5-Dimethyl-2-tolylazo-cyclohexane-1,3-dione (azo dye (ii)), have been studied from optical Kerr nonlinearity point of view. These materials were characterized by Ultraviolet-visible spectroscopy. Experiments were performed using a continous wave diode-pumped laser at 532 nm wavelength in three intensities of the laser beam. Nonlinear absorption (β), refractive index (n2) and third-order susceptibility (χ (3)) of dyes, were calculated. Nonlinear absorption coefficient of dyes have been calculated from two methods; 1) using theoretical fits and experimental data in the Z-scan technique, 2) using the strength of nonlinearity curves. The values of β obtained from both of the methods were approximately the same. The results demonstrated that azo dye (ii) displays better nonlinearity and has a lower two-photon absorption threshold than azo dye (i). Calculated parameter related to strength of nonlinearity for azo dye (ii) was higher than azo dye (i), It may be due to presence of methyl in azo dye (ii) instead of chlorine in azo dye (i). Furthermore, The measured values of third order susceptibility of azo dyes were from the order of 10-9 esu . These azo dyes can be suitable candidate for optical switching devices.

Development of Processible Electroactive Oligomers and Polymers

DTIC Science & Technology

1991-10-01

of structure and electroactive properties. Electroactive molecules including fused ring (ladder oligomers) dyes , squarylium -heterocyclic moieties...Electroactive molecules including fused ring (ladder oligomers) dyes , squarylium -heterocyclic moieties, phenylpolyenes, thienylpolyenes, carbocyanine dyes ...phenylpolyenes, thienylpolyenes, carbocyanine dyes , and tetraazaannulenes have also been synthetically incorporated into a variety of traditional

Optimization via specific fluorescence brightness of a receptor-targeted probe for optical imaging and positron emission tomography of sentinel lymph nodes

PubMed Central

Qin, Zhengtao; Hall, David J.; Liss, Michael A.; Hoh, Carl K.; Kane, Christopher J.; Wallace, Anne M.

2013-01-01

Abstract. The optical properties of a receptor-targeted probe designed for dual-modality mapping of the sentinel lymph node (SLN) was optimized. Specific fluorescence brightness was used as the design criterion, which was defined as the fluorescence brightness per mole of the contrast agent. Adjusting the molar ratio of the coupling reactants, IRDye 800CW-NHS-ester and tilmanocept, enabled us to control the number of fluorescent molecules attached to each tilmanocept, which was quantified by H1 nuclear magnetic resonance spectroscopy. Quantum yields and molar absorptivities were measured for unconjugated IRDye 800CW and IRDye 800CW-tilmanocept (800CW-tilmanocept) preparations at 0.7, 1.5, 2.3, 2.9, and 3.8 dyes per tilmanocept. Specific fluorescence brightness was calculated by multiplication of the quantum yield by the molar absorptivity and the number of dyes per tilmanocept. It predicted that the preparation with 2.3 dyes per tilmanocept would exhibit the brightest signal, which was confirmed by fluorescence intensity measurements using three optical imaging systems. When radiolabeled with Ga68 and injected into the footpads of mice, the probe identified SLNs by both fluorescence and positron emission tomography (PET) while maintaining high percent extraction by the SLN. These studies demonstrated the feasibility of 800CW-tilmanocept for multimodal SLN mapping via fluorescence and PET–computed tomography imaging. PMID:23958947

π-Expanded α,β-unsaturated ketones: synthesis, optical properties, and two-photon-induced polymerization.

PubMed

Nazir, Rashid; Bourquard, Florent; Balčiūnas, Evaldas; Smoleń, Sabina; Gray, David; Tkachenko, Nikolai V; Farsari, Maria; Gryko, Daniel T

2015-02-23

A library of π-expanded α,β-unsaturated ketones was designed and synthesized. They were prepared by a combination of Wittig reaction, Sonogashira reaction, and aldol condensation. It was further demonstrated that the double aldol condensation can be performed effectively for highly polarized styrene- and diphenylacetylene-derived aldehydes. The strategic placement of two dialkylamino groups at the periphery of D-π-A-π-D molecules resulted in dyes with excellent solubility. These ketones absorb light in the region 400-550 nm. Many of them display strong solvatochromism so that the emission ranges from 530-580 nm in toluene to the near-IR region in benzonitrile. Ketones based on cyclobutanone as central moieties display very high fluorescence quantum yields in nonpolar solvents, which decrease drastically in polar media. Photophysical studies of these new functional dyes revealed that they possess an enhanced two-photon absorption cross section when compared with simpler ketone derivatives. Due to strong polarization of the resulting dyes, values of two-photon absorption cross sections on the level of 200-300 GM at 800 nm were achieved, and thanks to that as well as the presence of the keto group, these new two-photon initiators display excellent performance so that the operating region is 5-75 mW in some cases. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Some fluorescence properties of dimethylaminochalcone and its novel cyclic analogues

NASA Astrophysics Data System (ADS)

Tomečková, Vladimíra; Poškrobová, Martina; Štefanišinová, Miroslava; Perjési, Pál

2009-12-01

This paper demonstrates the basic character (polarity, solubility, colour, absorption and fluorescence quantum yield) of synthetic dimethylaminochalcone ( 1) and its cyclic analogues measured in toluene, chloroform, dimethylsulfoxide and ethanol, which have been studied by absorption and fluorescence spectroscopy. The biologically active dye 4'-dimethylaminochalcone ( 1b) and its less flexible analogues 4-dimethylaminoindanone ( 2b), -tetralone ( 3b), and -benzosuberone ( 4b) are lipophilic molecules that displayed the best solubility in toluene and chloroform. The highest fluorescence and quantum yields of compounds 1 and 2 have been obtained in DMSO and chloroform. Quenching effect of fluorescence compounds ( 1- 4) has been studied in the mixture of the most polar organic solvents DMSO and water. In the presence of water, fluorescence of compound 1 has been quenched the best from all studied chalcones and emission maxima of molecules 1- 4 have been shifted to the longer wavelengths. Quenching effect of fluorescence by water was in order 1 > 2 > 3 > 4.

A polarized view on DNA under tension

NASA Astrophysics Data System (ADS)

van Mameren, Joost; Vermeulen, Karen; Wuite, Gijs J. L.; Peterman, Erwin J. G.

2018-03-01

In the past decades, sensitive fluorescence microscopy techniques have contributed significantly to our understanding of the dynamics of DNA. The specific labeling of DNA using intercalating dyes has allowed for quantitative measurement of the thermal fluctuations the polymers undergo. On the other hand, recent advances in single-molecule manipulation techniques have unraveled the mechanical and elastic properties of this intricate polymer. Here, we have combined these two approaches to study the conformational dynamics of DNA under a wide range of tensions. Using polarized fluorescence microscopy in conjunction with optical-tweezers-based manipulation of YOYO-intercalated DNA, we controllably align the YOYO dyes using DNA tension, enabling us to disentangle the rapid dynamics of the dyes from that of the DNA itself. With unprecedented control of the DNA alignment, we resolve an inconsistency in reports about the tilted orientation of intercalated dyes. We find that intercalated dyes are on average oriented perpendicular to the long axis of the DNA, yet undergo fast dynamics on the time scale of absorption and fluorescence emission. In the overstretching transition of double-stranded DNA, we do not observe changes in orientation or orientational dynamics of the dyes. Only beyond the overstretching transition, a considerable depolarization is observed, presumably caused by an average tilting of the DNA base pairs. Our combined approach thus contributes to the elucidation of unique features of the molecular dynamics of DNA.

Broadband energy transfer to sensitizing dyes by mobile quantum dot mediators in solar cells

PubMed Central

Adhyaksa, Gede Widia Pratama; Lee, Ga In; Baek, Se-Woong; Lee, Jung-Yong; Kang, Jeung Ku

2013-01-01

The efficiency of solar cells depends on absorption intensity of the photon collectors. Herein, mobile quantum dots (QDs) functionalized with thiol ligands in electrolyte are utilized into dye–sensitized solar cells. The QDs serve as mediators to receive and re–transmit energy to sensitized dyes, thus amplifying photon collection of sensitizing dyes in the visible range and enabling up–conversion of low-energy photons to higher-energy photons for dye absorption. The cell efficiency is boosted by dispersing QDs in electrolyte, thereby obviating the need for light scattering1 or plasmonic2 structures. Furthermore, optical spectroscopy and external quantum efficiency data reveal that resonance energy transfer due to the overlap between QD emission and dye absorption spectra becomes dominant when the QD bandgap is higher than the first excitonic peak of the dye, while co–sensitization resulting in a fast reduction of oxidized dyes is pronounced in the case of lower QD band gaps. PMID:24048384

The influence of material type and composition of TiO2- ZnO on manufacturing of paste for the application of DSSC

NASA Astrophysics Data System (ADS)

Retnaningsih, L.; Muliani, L.; Aggraini, P. N.; Hidayat, J.

2016-11-01

Research, fabrication and material selection for the application of Dye- sensitized solar cell (DSSC) has been performed on glass FTO (Flour Tin Oxide). The material is used in the form of TiO2 paste, TiO2 powder and ZnO powder. Dye-sensitized solar cell (DSSC), is a fotoelektrokimia-based solar cells where the absorption process light done by the dye molecules and the process of separation of inorganic semiconductor materials by charge of Titanium dioxide (TiO2) and Zinc oxide (ZnO). The purpose of this research is to know the exact composition of TiO2 and ZnO materials in order to produce the best efficiency with DSSC. On this research was done making prototype dye-sensitized solar cell using dye Z 907, and semiconductor nanoparticles TiO2 and ZnO powder that is made into a paste by mixing different composition in two variations of samples: A = ZnO (powder) + 40% TiO2 (powder) and B = 60% TiO2 (powder) (40%) + TiO2 (pasta) 60%. The second variation of this high efficiency is value at sample B i.e. TiO2 (powder) + 40% TiO2 (paste) of 60%.

Novel method for evaluation of natural dyes in DSSC

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

Lakshmi, M.; Kavitha, S.; Paul, Mercyleena

Dye sensitized Solar Cell (DSSC) is presently centered on Ruthenium based dyes. Recent research is diverted to explore the potential of natural dyes in replacing the conventional dyes. In this work we have chosen few natural dyes, which when coated on TiO{sub 2} leads to increase in absorption capacity of TiO{sub 2}. Co-relation of absorption and electrochemical properties of natural dyes gives a scientific insight of the probable performance of a dye, even without fabricating a cell. We have tried to compare this predictions based on HOMO-LUMO energy levels with the real cell performance. Measurements of cell parameters suggest thatmore » there is scope for further research in this area.« less

Optical properties of amyloid stained by Congo red: history and mechanisms.

PubMed

Howie, Alexander J; Brewer, Douglas B

2009-04-01

Amyloid stained by Congo red has striking optical properties that generally have been poorly described and inadequately explained, although they can be understood from principles of physical optics. Molecules of Congo red are orientated on amyloid fibrils, and so the dye becomes dichroic and birefringent. The birefringence varies with wavelength in accordance with a fundamental property of all light-transmitting materials called anomalous dispersion of the refractive index around an absorption peak. The combination of this and absorption of light, with modification by any additional birefringence in the optical system, explains the various colours that can be seen in Congo red-stained amyloid between crossed polariser and analyser, and also when the polariser and analyser are progressively uncrossed. These are called anomalous colours.

Nanorod-Based Fast-Response Pressure-Sensitive Paints

NASA Technical Reports Server (NTRS)

Bencic, Timothy; VanderWal, Randall

2007-01-01

A proposed program of research and development would be devoted to exploitation of nanomaterials in pressuresensitive paints (PSPs), which are used on wind-tunnel models for mapping surface pressures associated with flow fields. Heretofore, some success has been achieved in measuring steady-state pressures by use of PSPs, but success in measuring temporally varying pressures has been elusive because of the inherent slowness of the optical responses of these materials. A PSP contains a dye that luminesces in a suitable wavelength range in response to photoexcitation in a shorter wavelength range. The luminescence is quenched by oxygen at a rate proportional to the partial pressure of oxygen and thus proportional to the pressure of air. As a result, the intensity of luminescence varies inversely with the pressure of air. The major problem in developing a PSP that could be easily applied to a wind-tunnel model and could be useful for measuring rapidly varying pressure is to provide very high gas diffusivity for rapid, easy transport of oxygen to and from active dye molecules. Most PSPs include polymer-base binders, which limit the penetration of oxygen to dye molecules, thereby reducing responses to pressure fluctuations. The proposed incorporation of nanomaterials (somewhat more specifically, nanorods) would result in paints having nanostructured surfaces that, relative to conventional PSP surfaces, would afford easier and more nearly complete access of oxygen molecules to dye molecules. One measure of greater access is effective surface area: For a typical PSP as proposed applied to a given solid surface, the nanometer-scale structural features would result in an exposed surface area more than 100 times that of a conventional PSP, and the mass of proposed PSP needed to cover the surface would be less than tenth of the mass of the conventional PSP. One aspect of the proposed development would be to synthesize nanorods of Si/SiO2, in both tangle-mat and regular- array forms, by use of chemical vapor deposition (CVD) and wet chemical processes, respectively. The rods would be coated with a PSP dye, and the resulting PSP signals would be compared with those obtained from PSP dye coats on conventional support materials. Another aspect of the proposed development would be to seek to exploit the quantum properties of nanorods of a suitable semiconductor (possibly GaN), which would be synthesized by CVD. These quantum properties of semiconductor nanorods include narrow-wavelength-band optical absorption and emission characteristics that vary with temperature. The temperature sensitivity might enable simultaneous measurement of fluctuating temperature and pressure and to provide a temperature correction for the PSP response.

Method and apparatus for passive optical dosimeter comprising caged dye molecules

DOEpatents

Sandison, David R.

2001-07-03

A new class of ultraviolet dosimeters is made possible by exposing caged dye molecules, which generate a dye molecule on exposure to ultraviolet radiation, to an exterior environment. Applications include sunburn monitors, characterizing the UV exposure history of UV-sensitive materials, especially including structural plastics, and use in disposable `one-use` optical equipment, especially medical devices.

Marine green algae Codium iyengarii as a good bio-sorbent for elimination of reactive black 5 from aqueous solution.

PubMed

Azmat, Rafia

2014-09-01

The green seaweeds Codium iyengarii (C. iyengarii) was used to prepare as an adsorbent surface for the deletion of Reactive Black 5 (RB 5) from aqueous solution via adsorption. The batch technique was adopted under the optimal condition of amount of adsorbent, agitation time, concentration of dye, and at neutral and low pH. The depletion in concentration of the dye was monitored by Schimadzo 180 AUV/Visible spectrophotometer. It was initially monolayer adsorption, which showed multilayered formation later on with the passage of time at low and neutral pH. The Results displayed that adsorptive ability of C. iyengarii was 1.95-3.82mg/g with an elevation in primary application of dye contents (50ppm-70 ppm). The elimination data were well stable into the Langmuir and Freundlich adsorption isotherm equations. The Langmuir (R2=0.9848) and Freundlich (R2=0.9441) constants for biosorption of RB 5 on green algae were determined. The coefficient relation values suggested that the Langmuir isotherm was well fitted. It explained the interaction of surface molecules, which helps in well organization of dye molecules in a monolayer formation initially on algal biomass. The pseudo first and second order rate equations were applied to link the investigational statistics and found that the second order rate expression was found to be more suitable for both the models. The absorption spectrum of RB 5 before and after adsorption with respect to time was monitored which clearly indicate that C. iyengarii was much effective surface at very low quantity.

The effect of different π-bridge configuration on bi-anchored triphenylamine and phenyl modified triphenylamine based dyes for dye sensitized solar cell (DSSC) application: A theoretical approach.

PubMed

Pounraj, P; Mohankumar, V; Pandian, M Senthil; Ramasamy, P

2018-01-01

Twenty eight bi-anchored triphenylamine (TH-1 to TH-14) and phenyl modified triphenylamine (PH-TH-1 to PH-TH-14) based metal free organic dyes are designed for DSSC application. The electronic effect of different π-bridge configurations in donor-π-bridge-acceptor (D-π-A) 2 structure was theoretically simulated and verified using density functional theory (DFT) and time dependent density functional theory (TD-DFT). The triphenylamine and phenyl modified triphenylamine groups are used as donor and cyanoacrylic acid group is used as acceptor. Thiophene and cyanovinyl groups are used as π-bridge. The ground state molecular structure was optimized by density functional theory and the electronic absorption spectra were calculated by time dependent density functional theory. The light harvesting efficiency (LHE), dye regeneration energy (ΔG reg ) and electron injection energy (ΔG inject ) are determined by computational examination. It is observed that, when the number of π-bridge increases, the band gap of the dye decreases. Also the absorption maximum and molar extinction coefficient of the dyes are increased. Theoretical result shows that the thiophene-cyanovinyl and thiophene-thiophene-cyanovinyl-cyanovinyl configurations give broader and red shifted absorption spectrum compared to other configurations. Also the results of phenyl modified triphenylamine (PH-TH) dyes clearly show better absorption and dye regeneration energy compared to TH dyes. Copyright © 2017 Elsevier Inc. All rights reserved.

Monodispersed Zinc Oxide Nanoparticle-Dye Dyads and Triads

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

Gladfelter, Wayne L.; Blank, David A.; Mann, Kent R.

The overall energy conversion efficiency of photovoltaic cells depends on the combined efficiencies of light absorption, charge separation and charge transport. Dye-sensitized solar cells are photovoltaic devices in which a molecular dye absorbs light and uses this energy to initiate charge separation. The most efficient dye-sensitized solar cells (DSSCs) use nanocrystal titanium dioxide films to which are attached ruthenium complexes. Numerous studies have provided valuable insight into the dynamics of these and analogous photosystems, but the lack of site homogeneity in binding dye molecules to metal oxide films and nanocrystals (NCs) is a significant impediment to extracting fundamental details aboutmore » the electron transfer across the interface. Although zinc oxide is emerging as a potential semiconducting component in DSSCs, there is less known about the factors controlling charge separation across the dye/ZnO interface. Zinc oxide crystallizes in the wurtzite lattice and has a band gap of 3.37 eV. One of the features that makes ZnO especially attractive is the remarkable ability to control the morphology of the films. Using solution deposition processes, one can prepare NCs, nanorods and nanowires having a variety of shapes and dimensions. This project solved problems associated with film heterogeneity through the use of dispersible sensitizer/ZnO NC ensembles. The overarching goal of this research was to study the relationship between structure, energetics and dynamics in a set of synthetically controlled donor-acceptor dyads and triads. These studies provided access to unprecedented understanding of the light absorption and charge transfer steps that lie at the heart of DSSCs, thus enabling significant future advances in cell efficiencies. The approach began with the construction of well-defined dye-NC dyads that were sufficiently dispersible to allow the use of state of the art pulsed laser spectroscopic and kinetic methods to understand the charge transfer events at a fundamental level. This was combined with the synthesis of a broad range of sensitizers that provide systematic variation of the energetics, excited state dynamics, structure and interfacial bonding. The key is that the monodisperse nature and high dispersibility of the ZnO NCs made these experiments reproducible; in essence, the measurements were on discrete molecular species rather than on the complicated mixtures that resulted from the typical fabrication of functional photovoltaic cells. The monodispersed nature of the NCs also allowed the use of quantum confinement to investigate the role of donor/acceptor energetic alignment in chemically identical systems. The results added significantly to our basic understanding of energy and charge transfer events at molecule-semiconductor interfaces and will help the R&D community realize zinc oxide's full potential in solar cell applications.« less

Theoretical Study of Effect of Introducing π-Conjugation on Efficiency of Dye-Sensitized Solar Cell.

PubMed

Lee, Geon Hyeong; Kim, Young Sik

2018-09-01

In this study, phenoxazine (PXZ)-based dye sensitizers with triphenylamine (TPA) as a dual-electron donor and thiophen and benzothiadiazole (BTD) or 4,7-diethynylbenzo[c][1,2,5]thiadiazole (DEBT) as an electron acceptor (dye1, dye2, and dye3) were designed and investigated. dye3 can significantly stabilize the lowest unoccupied molecular orbital (LUMO) energy level of an organic dye. We used density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations to better understand the factors responsible for the photovoltaic performance. The absorption spectrum of the dyes showed different forms because of the different energy levels of the molecular orbital (MO) of each dye and the intramolecular energy transfer (EnT). Among the three dyes, dye3 showed greater red-shift, broader absorption spectra, and higher molar extinction coefficient. These results indicate that adding a withdrawing unit and π-conjugation to a dye can result in good photovoltaic properties for dye-sensitized solar cells (DSSCs).

Molecular modification of coumarin dyes for more efficient dye sensitized solar cells

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

Sanchez-de-Armas, Rocio; San-Miguel, Miguel A.; Oviedo, Jaime

2012-05-21

In this work, new coumarin based dyes for dye sensitized solar cells (DSSC) have been designed by introducing several substituent groups in different positions of the NKX-2311 structure. Two types of substitutions have been considered: the introduction of three electron-donating groups (-OH, -NH{sub 2}, and -OCH{sub 3}) and two different substituents with steric effect: -CH{sub 2}-CH{sub 2}-CH{sub 2}- and -CH{sub 2}-HC=CH-. The electronic absorption spectra (position and width of the first band and absorption threshold) and the position of the LUMO level related to the conduction band have been used as theoretical criteria to evaluate the efficiency of the newmore » dyes. The introduction of a -NH{sub 2} group produces a redshift of the absorption maximum position and the absorption threshold, which could improve the cell efficiency. In contrast, the introduction of -CH{sub 2}-CH{sub 2}-CH{sub 2}- does not modify significantly the electronic structure of NKX-2311, but it might prevent aggregation. Finally, -CH{sub 2}-HC=CH- produces important changes both in the electronic spectrum and in the electronic structure of the dye, and it would be expected as an improvement of cell efficiency for these dyes.« less

Intracavity absorption with a continuous wave dye laser - Quantification for a narrowband absorber

NASA Technical Reports Server (NTRS)

Brobst, William D.; Allen, John E., Jr.

1987-01-01

An experimental investigation of the dependence of intracavity absorption on factors including transition strength, concentration, absorber path length, and pump power is presented for a CW dye laser with a narrow-band absorber (NO2). A Beer-Lambert type relationship is found over a small but useful range of these parameters. Quantitative measurement of intracavity absorption from the dye laser spectral profiles showed enhancements up to 12,000 (for pump powers near lasing threshold) when compared to extracavity measurements. The definition of an intracavity absorption coefficient allowed the determination of accurate transition strength ratios, demonstrating the reliability of the method.

NIR fluorescent dyes: versatile vehicles for marker and probe applications

NASA Astrophysics Data System (ADS)

Patonay, Gabor; Chapman, Gala; Beckford, Garfield; Henary, Maged

2013-02-01

The use of the NIR spectral region (650-900 nm) is advantageous due to the inherently lower background interference and the high molar absorptivities of NIR chromophores. Near-Infrared (NIR) dyes are increasingly used in the biological and medical field. The binding characteristics of NIR dyes to biomolecules are possibly controlled by several factors, including hydrophobicity, size and charge just to mention a few parameters. Binding characteristics of symmetric carbocyanines and found that the hydrophobic nature of the NIR dye is only partially responsible for the binding strength. Upon binding to biomolecules significant fluorescence enhancement can be observed for symmetrical carbocyanines. This fluorescence amplification facilitates the detection of the NIR dye and enhances its utility as NIR reporter. This manuscript discusses some probe and marker applications of such NIR fluorescent dyes. One application discussed here is the use of NIR dyes as markers. For labeling applications the fluorescence intensity of the NIR fluorescent label can significantly be increased by enclosing several dye molecules in nanoparticles. To decrease self quenching dyes that have relatively large Stokes' shift needs to be used. This is achieved by substituting meso position halogens with amino moiety. This substitution can also serve as a linker to covalently attach the dye molecule to the nanoparticle backbone. We report here on the preparation of NIR fluorescent silica nanoparticles. Silica nanoparticles that are modified with aminoreactive moieties can be used as bright fluorescent labels in bioanalytical applications. A new bioanalytical technique to detect and monitor the catalytic activity of the sulfur assimilating enzyme using NIR dyes is reported as well. In this spectroscopic bioanalytical assay a family of Fischer based n-butyl sulfonate substituted dyes that exhibit distinct variation in absorbance and fluorescence properties and strong binding to serum albumin as its sulfonic acid moiety is modified to less water soluble moiety was identified. In polar solvents, these water soluble compounds are strongly fluorescent, however form the less soluble aggregated species with virtual loss of fluorescence when the sulfonate groups are cleaved by enzymatic activity to form the corresponding straight chain alkyl aldehyde derivatives. To achieve this conversion in vitro photo-reduced riboflavin mononucleotide (FMN) with a glucose/ glucose-oxygenase oxygen scavenging system was utilized. The reduced FMN serves as a key substrate in the enzymatic desulfonation. Once the FMNH2 was produced the desulfonation reaction was characterized by using Laser Induced Fluorescence Capillary Zone Electropheresis (LIF-CZE). This method can be utilized as an assay to detect the enzyme activity in vitro with the possibilities of in vivo applications.

Effect of marine derived deoxyribonucleic acid on nonlinear optical properties of PicoGreen dye

NASA Astrophysics Data System (ADS)

Pradeep, C.; Mathew, S.; Nithyaja, B.; Radhakrishnan, P.; Nampoori, V. P. N.

2013-06-01

We have investigated the effect of DNA on nonlinear absorption of PicoGreen dye using single beam open aperture Z-scan technique in nanosecond regime. We observed reverse saturable absorption at 532 nm for PicoGreen without DNA. In the presence of DNA, the sample begins to behave like saturable absorbers and this effect increased as the concentration of DNA was increased. The dye-intercalated DNA showed SA characteristics near the focus but exhibited RSA characteristics at the focus. Theoretical analysis has been performed using a two-photon absorption model based on nonlinear absorption coefficient and saturation intensity. Such tailoring of optical nonlinear absorption in PicoGreen makes it a potential candidate for photonic application.

High resolution absorption cross sections for the A2Pi-X2Pi system of ClO

NASA Technical Reports Server (NTRS)

Wine, P. H.; Ravishankara, A. R.; Philen, D. L.; Davis, D. D.; Watson, R. T.

1977-01-01

High-resolution ultraviolet absorption cross-sections for the ClO molecule are obtained, with the aim of facilitating studies of ozone depletion resulting from the injection of chlorofluorocarbons into the atmosphere. The spectroscopic analysis, which involves a frequency-doubled tunable dye laser with a bandwidth of 0.015 A, is described. Studies of the rotational lines of the ClO A 2Pi 3/2-X2Pi 3/2 9-10 band were conducted. Peak cross-sections for the P and R lines of the 9-0 band are found to be 10.0, 9.6, 8.6, 10.6, 10.3, and 9.2 times ten to the negative seventeenth power cm squared, with estimated accuracy of plus or minus 25%. Problems in distinguishing between Cl-35 and Cl-37 absorption are also considered.

Enhanced performances of dye-sensitized solar cells based on Au-TiO2 and Ag-TiO2 plasmonic hybrid nanocomposites

NASA Astrophysics Data System (ADS)

Ran, Huili; Fan, Jiajie; Zhang, Xiaoli; Mao, Jing; Shao, Guosheng

2018-02-01

Novel double-layer films were prepared and applied to dye-sensitized solar cells (DSSCs) using commercial TiO2 nanoparticles as a bonding underlayer and noble metal (Au and Ag) nanoparticles (NP) and nanowires (NW) incorporated to hybrid TiO2 composites, consisting of 3 dimensional (3D) hierarchical microspheres, 3D hollow spheres, 2 dimensional (2D) nanosheets and commercial P25 nanoparticles, as multifunctional light scattering overlayer. The influence of Au NP, Ag NP, Au NW, and Ag NW on of microstructures of the film electrodes and the photovoltaic (PV) performances of DSSCs was investigated. The result revealed that the ranges and intensity of sunlight absorption, the photo capture ability for dye molecules of the hybrid nanocomposite film electrodes, and the photoelectric conversion efficiency (PCE) of the cells were all significantly enhanced due to the plasmonic effect of the noble metal nanostructures. All composite DSSCs with noble metal nanostructures have higher PCE than the pure TiO2 solar cell. This is attributed the improved electron transport of the noble metal nanostructures, and the improvement of light absorption because of their local surface plasmon resonance (LSPR) effect. Under optical conditions, a PCE of 5.74% was obtained in the TiO2-AgNW DSSC, representing a 25.3% enhancement compared to a reference solar cell based on pure TiO2 film (4.58%). The main reason of the advancement is the improved electron transport of AgNW, the light absorption enhancement on account of the LSPR effect of AgNW, and increased light scattering due to the incorporation of the large one dimensional AgNWs within the photo-anode.

High-Yield Excited Triplet States in Pentacene Self-Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission.

PubMed

Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku

2016-04-18

One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tulane/Xavier Vaccine Development/Engineering Project

DTIC Science & Technology

2009-02-01

spectroscopic studies with polar dyes (e.g. proflavine ) have verified these compounds’ ability to encapsulate and solvate small polar dye molecules in...systems. Fluorescent microscopy studies verify that they significantly enhance the transport of polar small molecules ( proflavin dye) through

Self-Assembly of Optical Molecules with Supramolecular Concepts

PubMed Central

Okamoto, Ken; Chithra, Parayalil; Richards, Gary J.; Hill, Jonathan P.; Ariga, Katsuhiko

2009-01-01

Fabrication of nano-sized objects is one of the most important issues in nanoscience and nanotechnology. Soft nanomaterials with flexible properties have been given much attention and can be obtained through bottom-up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and techniques. Among the various functional molecules, dyes have become important materials in certain areas of nanotechnology and their self-assembling behaviors have been actively researched. In this short review, we briefly introduce recent progress in self-assembly of optical molecules and dyes, based mainly on supramolecular concepts. The introduced examples are classified into four categories: self-assembly of (i) low-molecular-weight dyes and (ii) polymeric dyes and dye self-assembly (iii) in nanoscale architectures and (iv) at surfaces. PMID:19564931

Conversion efficiency versus sensitizer for electrospun TiO2 nanorod electrodes in dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Jose, R.; Kumar, A.; Thavasi, V.; Ramakrishna, S.

2008-10-01

The electrochemical and optical properties of three indoline dyes, namely C35H28N2O2 (D131), C37H30N2O3S2 (D102), and C42H35N3O4S3 (D149), were studied and compared with that of the N3 dye. D131 has the largest bandgap and lowest unoccupied molecular orbital (LUMO) energies compared to the other dyes. A size-dependent variation in the absorptivity of the indoline dyes was observed—the absorptivity increased with increase in the molecular size. The dyes were anchored onto TiO2 nanorods. The TiO2 nanorods were obtained by electrospinning a polymeric solution containing titanium isopropoxide and polyvinylpyrrolidone and subsequent sintering of the as-spun composite fibers. Absorption spectral measurements of the dye-anchored TiO2 showed blue shifts in the excitonic transition of the indoline dyes, the magnitude of which increased with decrease in the molecular size. Dye-sensitized solar cells (DSSCs) were fabricated using the indoline dyes, TiO2 nanorods, and iodide/triiodide electrolyte. The D131 dye showed comparable energy conversion efficiency (η) to that of the N3 dye. A systematic change in the short circuit current density (JSC) and η of the indoline DSSCs was observed. The observed variation in JC is most likely originated from the difference in the electronic coupling strengths between the dye and the TiO2.

Phenolic dyes as nonbleachable absorbers compatible with novolac resins for linewidth control in photoresists

DOEpatents

Renschler, C.L.

1986-11-25

Photoresist techniques and compositions are provided employing curcumin as an absorptive dye for the purpose of reducing linewidth non-uniformity caused by scattered and reflective light from the substrate-resist interface. The photoresist compositions containing curcumin as the absorptive dye are used in the production of microelectronic circuitry by both single layer and multilayer photoresist techniques.

Fluorescent measurements in whole blood and plasma using red-emitting dyes

NASA Astrophysics Data System (ADS)

Abugo, Omoefe O.; Herman, Petr; Lakowicz, Joseph R.

2000-04-01

We have determined the fluorescence characteristics of albumin blue 670 and Rhodamine 800 in plasma and blood in order to test the feasibility of making direct fluorescence sensing measurements in blood. These dyes were used because of their absorption in the red/NIR where absorption by hemoglobin is minimized. Front face illumination and detection was used to minimize absorption and scattering during measurement. Fluorescence emission was observed for these dyes in plasma and blood. Attenuation of the fluorescence emission was observed in blood because of hemoglobin absorption. Using frequency domain fluorometry, we recovered the expected lifetime parameters for both dyes in blood and plasma. We were able to quantify HSA concentrations using changes in the mean lifetime of AB670, a dye previously shown to bind preferentially to HSA. Rh800 concentrations in plasma and blood were also determined using modulation sensing. Anisotropy measurements revealed high Anisotropy for these dyes in plasma and blood. It also showed an increase in the anisotropy of AB670 with increase in HSA concentration in the presence of red blood cells. These results indicate that qualitative and quantitative fluorescence measurements can be made directly in blood without the need to process the blood.

Part 1: Synthesis and visible absorption spectra of some new monoazo dyes derived from ethyl 2-amino-4-(4";-substitutedphenyl)thiophenes

NASA Astrophysics Data System (ADS)

Babür, Banu; Ertan, Nermin

2014-10-01

Series of monoazo dyes from some ethyl 2-amino-4-(4";-substitutedphenyl) thiophenes were prepared and characterized. The structure of the substances was confirmed by FT-IR, 1H NMR and mass spectroscopic techniques. The relationship among the structure of the dyes, their absorption characteristics and the solvatochromic and halochromic behaviors of the dyes were investigated. Introduction of electron-accepting substituent into the diazo moiety results in large bathochromic shifts in all solvents used. The dyes exhibited positive solvatochromism and their solvatochromic properties were discussed in relation to tautomerism.

Single-molecule studies of oligomer extraction and uptake of dyes in poly(dimethylsiloxane) films.

PubMed

Lange, Jeffrey J; Collinson, Maryanne M; Culbertson, Christopher T; Higgins, Daniel A

2009-12-15

Single-molecule microscopic methods were used to probe the uptake, mobility, and entrapment of dye molecules in cured poly(dimethylsiloxane) (PDMS) films as a function of oligomer extraction. The results are relevant to the use of PDMS in microfluidic separations, pervaporation, solid-phase microextraction, and nanofiltration. PDMS films were prepared by spin-casting dilute solutions of Sylgard 184 onto glass coverslips, yielding approximately 1.4 microm thick films after curing. Residual oligomers were subsequently extracted from the films by "spin extraction". In this procedure, 200 microL aliquots of isopropyl alcohol were repeatedly dropped onto the film surface and spun off at 2000 rpm. Samples extracted 5, 10, 20, and 40 times were investigated. Dye molecules were loaded into these films by spin-casting nanomolar dye solutions onto the films. Both neutral perylene diimide (N,N'-bis(butoxypropyl)perylene-3,4,9,10-tetracarboxylic diimide) and cationic rhodamine 6G (R6G) dyes were employed. The films were imaged by confocal fluorescence microscopy. The images obtained depict nonzero populations of fixed and mobile molecules in all films. Cross-correlation methods were used to quantitatively determine the population of fixed molecules in a given region, while a Bayesian burst analysis was used to obtain the total population of molecules. The results show that the total amount of dye loaded increases with increased oligomer extraction, while the relative populations of fixed and mobile molecules decrease and increase, respectively. Bulk R6G data also show greater dye loading with increased oligomer extraction.

Synthesis and spectroscopic properties of silica-dye-semiconductor nanocrystal hybrid particles.

PubMed

Ren, Ting; Erker, Wolfgang; Basché, Thomas; Schärtl, Wolfgang

2010-12-07

We prepared silica-dye-nanocrystal hybrid particles and studied the energy transfer from semiconductor nanocrystals (= donor) to organic dye molecules (= acceptor). Multishell CdSe/CdS/ZnS semiconductor nanocrystals were adsorbed onto monodisperse Stöber silica particles with an outer silica shell of thickness 2-23 nm containing organic dye molecules (Texas Red). The thickness of this dye layer has a strong effect on the energy transfer efficiency, which is explained by the increase in the number of dye molecules homogeneously distributed within the silica shell, in combination with an enhanced surface adsorption of nanocrystals with increasing dye amount. Our conclusions were underlined by comparison of the experimental results with numerically calculated FRET efficiencies and by control experiments confirming attractive interaction between the nanocrystals and Texas Red freely dissolved in solution.

Preparation of 6-hydroxyindolines and their use for preparation of novel laser dyes

DOEpatents

Field, George F.; Hammond, Peter R.

1993-01-01

A novel method for the synthesis of 6-hydroxyindolines and new fluorescent dyes produced therefrom, which dyes are ring-constrained indoline-based rhodamine class dyes. These dyes have absorption and emission spectra which make them particularly useful in certain dye laser applications.

Single wall carbon nanotubes dispersion study of different dye molecules and chitosan

NASA Astrophysics Data System (ADS)

Ramli, Muhammad M.; Isa, Siti S. Mat; Abdullah, M. M. A. B.; Murad, S. A. Z.

2017-09-01

Carbon Nanotubes (CNTs) is known for their hydrophobicity ability. However, this ability can become the bottleneck for the application of CNTs where a highly dispersion of materials are needed. In this project, different dispersing agents were investigated namely dye molecules and chitosan. Three different dyes are studied with different concentration, including 0.05 % of chitosan. The dispersion quality is determined by examining through UV-Vis-NIR. The best dispersion quality investigated here is when the concentration of dye molecules is higher, which is around 2.5 mM.

Absorption bleaching of squarylium dye J aggregates via a two-photon excitation process

NASA Astrophysics Data System (ADS)

Furuki, Makoto; Tian, Minquan; Sato, Yasuhiro; Pu, Lyong Sun; Tatsuura, Satoshi; Abe, Shuji

2001-08-01

Squarylium dye J aggregates exhibit ultrafast nonlinear optical response of absorption saturation at the resonant wavelength of 770 nm. We studied the two-photon excitation process of J aggregates. By fluorescence measurement, we found the two-photon absorption band at 1.3 μm, which was different from that of the dye solution at 1.2 μm. Absorption saturation at 770 nm via a two-photon excitation process was observed by two-photon resonant excitation at 1.3 μm and also by off-resonant excitation at 1.55 μm, suggesting the possibility of J aggregates for optical switching materials working at the wavelength used in optical communications.

Phenolic dyes as nonbleachable absorbers compatible with novolac resins for linewidth control in photoresists

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

Renschler, C.L.

1988-10-17

Photoresist techniques and compositions are provided employing curcumin as an absorptive dye for the purpose of reducing linewidth non-uniformity caused by scattered and reflective light from the substrate-resist interface. The photoresist compositions containing curcumin as the absorptive dye are used in the production of microelectronic circuitry by both single layer and multilayer photoresist techniques. 2 figs.

Band-engineering of TiO2 as a wide-band gap semiconductor using organic chromophore dyes

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Kartini, I.; Ramelan, A. H.; Saputri, L. N. M. Z.; Munawaroh, H.

2017-07-01

Bond-engineering as applied to semiconductor materials refers to the manipulation of the energy bands in order to control charge transfer processes in a device. When the device in question is a photoelectrochemical cell, the charges affected by drift become the focus of the study. The ideal band gap of semiconductors for enhancement of photocatalyst activity can be lowered to match with visible light absorption and the location of conduction Band (CB) should be raised to meet the reducing capacity. Otherwise, by the addition of the chromofor organic dyes, the wide-band gab can be influences by interacation resulting between TiO2 surface and the dyes. We have done the impruvisation wide-band gap of TiO2 by the addition of organic chromophore dye, and the addition of transition metal dopand. The TiO2 morphology influence the light absorption as well as the surface modification. The organic chromophore dye was syntesized by formation complexes compound of Co(PAR)(SiPA)(PAR)= 4-(2-piridylazoresorcinol), SiPA = Silyl propil amine). The result showed that the chromophore groups adsorbed onto TiO2 surface can increase the visible light absorption of wide-band gab semiconductor. Initial absorption of a chromophore will affect light penetration into the material surfaces. The use of photonic material as a solar cell shows this phenomenon clearly from the IPCE (incident photon to current conversion efficiency) measurement data. Organic chromophore dyes of Co(PAR)(SiPA) exhibited the long wavelength absorption character compared to the N719 dye (from Dyesol).

Preparation of 6-hydroxyindolines and their use for preparation of novel laser dyes

DOEpatents

Field, G.F.; Hammond, P.R.

1993-10-26

A novel method is described for the synthesis of 6-hydroxyindolines and new fluorescent dyes produced therefrom, which dyes are ring-constrained indoline-based rhodamine class dyes. These dyes have absorption and emission spectra which make them particularly useful in certain dye laser applications.

Novel durable bio-photocatalyst purifiers, a non-heterogeneous mechanism: accelerated entrapped dye degradation into structural polysiloxane-shield nano-reactors.

PubMed

Dastjerdi, Roya; Montazer, Majid; Shahsavan, Shadi; Böttcher, Horst; Moghadam, M B; Sarsour, Jamal

2013-01-01

This research has designed innovative Ag/TiO(2) polysiloxane-shield nano-reactors on the PET fabric to develop novel durable bio-photocatalyst purifiers. To create these very fine nano-reactors, oppositely surface charged multiple size nanoparticles have been applied accompanied with a crosslinkable amino-functionalized polysiloxane (XPs) emulsion. Investigation of photocatalytic dye decolorization efficiency revealed a non-heterogeneous mechanism including an accelerated degradation of entrapped dye molecules into the structural polysiloxane-shield nano-reactors. In fact, dye molecules can be adsorbed by both Ag and XPs due to their electrostatic interactions and/or even via forming a complex with them especially with silver NPs. The absorbed dye and active oxygen species generated by TiO(2) were entrapped by polysiloxane shelter and the presence of silver nanoparticles further attract the negative oxygen species closer to the adsorbed dye molecules. In this way, the dye molecules are in close contact with concentrated active oxygen species into the created nano-reactors. This provides an accelerated degradation of dye molecules. This non-heterogeneous mechanism has been detected on the sample containing all of the three components. Increasing the concentration of Ag and XPs accelerated the second step beginning with an enhanced rate. Further, the treated samples also showed an excellent antibacterial activity. Copyright © 2012 Elsevier B.V. All rights reserved.

Analysis of the Spectroscopic Aspects of Cationic Dye Basic Orange 21.

PubMed

Eizig, Zehavit; Major, Dan T; Kasdan, Harvey L; Afrimzon, Elena; Zurgil, Naomi; Sobolev, Maria; Deutsch, Mordechai

2015-09-24

Spectroscopic properties of cationic dye basic orange 21 (BO21) in solutions, in solids, and within leukocytes were examined. Results obtained with solutions indicate that influence of variables such as pH, viscosity, salt composition, and various proteins on the absorption spectrum of BO21 is negligible. However, in the presence of heparin, a blue shift (484-465 nm) is observed, which is attributed to the aggregation of BO21 on the polyanion. Applying density functional theory demonstrates that in aqueous solutions (a) the formation of BO21 oligomers is thermodynamically favorable, they are oriented in an antiparallel dipolar arrangement, and their binding energies are lower than those of parallel dipolar arrangements, (b) association between BO21 aggregates and heparin is highly favorable, and (c) the blue shift is due to the mixing of π → π* transitions caused by BO21 molecule stacking. However, when embedded in basophils, the absorption spectra of intracellular BO21 is extremely red-shifted, with two peaks (at 505 and 550 nm) found to be attributed to BO21 and the BO21-heparin complex, respectively, which are intracellularly hosted in nonaqueous environments. Initial evidence of the ability to differentiate between leukocyte types by BO21 is presented.

Optical properties of natural dyes on the dye-sensitized solar cells (DSSC) performance

NASA Astrophysics Data System (ADS)

Pratiwi, D. D.; Nurosyid, F.; Supriyanto, A.; Suryana, R.

2016-11-01

This study reported several natural dyes for application in dye-sensitized solar cells (DSSC). This study aims was to determine the effect of optical absorption properties of natural dyes on efficiency of DSSC. The sandwich structure of DSSC consist of TiO2 as working electrode, carbon layer as counter electrode, natural dyes as photosensitizer, and electrolyte as electron transfer media. The natural dyes used in this experiment were extracted from dragon fruit anthocyanin, mangosteen peels anthocyanin, and red cabbage anthocyanin. The absorbance of dyes solutions and the adsorption of the dye on the surface of TiO2 were characterized using UV-Vis spectrophotometer, the quantum efficiency versus wavelength was characterized using incident photon-to-current efficiency (IPCE) measurement system, and the efficiency of DSSC was calculated using I-V meter. UV-Vis characteristic curves showed that wavelength absorption of anthocyanin dye of red cabbage was 450 - 580 nm, anthocyanin of mangosteen peels was 400 - 480 nm, and anthocyanin of dragon fruit was 400 - 650 nm. Absorption spectra of the dye adsorption on the surface of TiO2 which was resulted in the highest absorbance of red cabbage anthocyanin. IPCE characteristic curves with anthocyanin dye of red cabbage, mangosteen peels anthocyanin, and dragon fruit anthocyanin resulted quantum efficiency of 0.058%; 0.047%; and 0.043%, respectively at wavelength maximum about 430 nm. I-V characteristic curves with anthocyanin dye of red cabbage, mangosteen peels anthocyanin, and dragon fruit anthocyanin resulted efficiency of 0.054%; 0.042%; and 0.024%, respectively.

Photo-induced interaction of thioglycolic acid (TGA)-capped CdTe quantum dots with cyanine dyes

NASA Astrophysics Data System (ADS)

Abdelbar, Mostafa F.; Fayed, Tarek A.; Meaz, Talaat M.; Ebeid, El-Zeiny M.

2016-11-01

The photo-induced interaction of three different sizes of thioglycolic acid (TGA)-capped CdTe quantum dots (CdTe QDs) with two monomethine cyanine dyes belonging to the thiazole orange (TO) family has been studied. Positively charged cyanines interact with QDs surface which is negatively charged due to capping agent carboxylate ions. The energy transfer parameters including Stern-Volmer constant, Ksv, number of binding sites, n, quenching sphere radius, r, the critical energy transfer distance, R0, and energy transfer efficiencies, E have been calculated. The effect of structure and the number of aggregating molecules have been studied as a function of CdTe QDs particle size. Combining organic and inorganic semiconductors leads to increase of the effective absorption cross section of the QDs which can be utilized in novel nanoscale designs for light-emitting, photovoltaic and sensor applications. A synthesized triplet emission of the studied dyes was observed using CdTe QDs as donors and this is expected to play a potential role in molecular oxygen sensitization and in photodynamic therapy (PDT) applications.

A dipeptide-based superhydrogel: Removal of toxic dyes and heavy metal ions from waste water.

PubMed

Nandi, Nibedita; Baral, Abhishek; Basu, Kingshuk; Roy, Subhasish; Banerjee, Arindam

2017-01-01

A short peptide-based molecule has been found to form a strong hydrogel at phosphate buffer solution of pH 7.46. The hydrogel has been characterized thoroughly using various techniques including field emission scanning electron microscopy (FE-SEM), wide angle powder X-ray diffraction (PXRD), and rheological analysis. It has been observed from FE-SEM images that entangled nanofiber network is responsible for gelation. Rheological investigation demonstrates that the self-assembly of this synthetic dipeptide results in the formation of mechanically strong hydrogel with storage modulus (G') around 10 4 Pa. This gel has been used for removing both cationic and anionic toxic organic dyes (Brilliant Blue, Congo red, Malachite Green, Rhodamine B) and metal ions (Co 2+ and Ni 2+ ) from waste water. Moreover, only a small amount of the gelator is required (less than 1 mg/mL) for preparation of this superhydrogel and even this hydrogel can be reused three times for dye/metal ion absorption. This signifies the importance of the hydrogel towards waste water management. © 2016 Wiley Periodicals, Inc.

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.

Investigation of the influence of coadsorbent dye upon the interfacial structure of dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Honda, M.; Yanagida, M.; Han, L.; Miyano, K.

2014-11-01

The interface between Ru(tcterpy)(NCS)3TBA2 [black dye (BD); tcterpy = 4,4',4″-tricarboxy-2,2':6',2″-terpyridine, NCS = thiocyanato, TBA = tetrabutylammonium cation] and nanocrystalline TiO2, as found in dye-sensitized solar cells, is investigated by soft-X-ray synchrotron radiation and compared with the adsorption structure of cis-Ru(Hdcbpy)2(NCS)2TBA2 (N719; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) on TiO2 to elucidate the relationship between the adsorption mode of BD and the photocurrent with and without coadsorbed indoline dye D131. The depth profile is characterized with X-ray photoelectron spectroscopy and S K-edge X-ray absorption fine structure using synchrotron radiation. Both datasets indicate that one of the isothiocyanate groups of BD interacts with TiO2 via its S atom when the dye is adsorbed from a single-component solution. In contrast, the interaction is slightly suppressed when D131 is coadsorbed, indicated by the fact that the presence of D131 changes the adsorption mode of BD. Based upon these results, the number of BD dye molecules interacting with the substrate is shown to decrease by 10% when D131 is coadsorbed, and the dissociation is shown to be related to the short-circuit photocurrent in the 600-800 nm region. The design of a procedure to promote the preferential adsorption of D131 therefore leads to an improvement of the short-circuit current and conversion efficiency.

Interaction Between Cyanine Dye IR-783 and Polystyrene Nanoparticles in Solution.

PubMed

Zhang, Yunzhi; Xu, Hui; Casabianca, Leah B

2018-05-17

The interactions between small molecule drugs or dyes and nanoparticles are important to the use of nanoparticles in medicine. Noncovalent adsorption of dyes on nanoparticle surfaces is also important to the development of nanoparticle dual-use imaging contrast agents. In the present work, solution-state NMR is used to examine the noncovalent interaction between a near-infrared cyanine dye and the surface of polystyrene nanoparticles in solution. Using 1D proton NMR, we can approximate the number of dye molecules that associate with each nanoparticle for different sized nanoparticles. Saturation-Transfer Difference (STD)-NMR was also used to show that protons near the positively-charged nitrogen in the dye are more strongly associated with the negatively-charged nanoparticle surface than protons near the negatively-charged sulfate groups of the dye. The methods described here can be used to study similar drug or dye molecules interacting with the surface of organic nanoparticles. This article is protected by copyright. All rights reserved.

Tunable lasers and their application in analytical chemistry

NASA Technical Reports Server (NTRS)

Steinfeld, J. I.

1975-01-01

The impact that laser techniques might have in chemical analysis is examined. Absorption, scattering, and heterodyne detection is considered. Particular emphasis is placed on the advantages of using frequency-tunable sources, and dye solution lasers are regarded as the outstanding example of this type of laser. Types of spectroscopy that can be carried out with lasers are discussed along with the ultimate sensitivity or minimum detectable concentration of molecules that can be achieved with each method. Analytical applications include laser microprobe analysis, remote sensing and instrumental methods such as laser-Raman spectroscopy, atomic absorption/fluorescence spectrometry, fluorescence assay techniques, optoacoustic spectroscopy, and polarization measurements. The application of lasers to spectroscopic methods of analysis would seem to be a rewarding field both for research in analytical chemistry and for investments in instrument manufacturing.

Synthesis, spectral features and biological activity of some novel hetarylazo dyes derived from 6-amino-1,3-dimethyluracil

NASA Astrophysics Data System (ADS)

Yousefi, Hessamoddin; Yahyazadeh, Asieh; Yazdanbakhsh, Mohammad Reza; Rassa, Mehdi; Moradi-e-Rufchahi, Enayat O.'llah

2012-05-01

A series of hetarylazoaminouracil dyes were prepared by coupling of 6-amino-1,3-dimethyluracil with eight diazotized heterocyclic amines in nitrosyl sulphuric acid. The prepared azo dyes were characterized by UV-Vis, FT-IR, 13C NMR, 1H NMR spectroscopic techniques and elemental analysis. The solvatochromism of dyes was evaluated with respect to wavelength of maximum absorption (λmax) in seven solvents with different polarities: acetic acid, methanol, water, chloroform, acetonitrile, dimethyl sulfoxide and dimethyl formamide. The effects of acid, base and concentration of the dye on the visible absorption spectra were also reported. In addition, the antimicrobial activity of the synthesized dyes was evaluated on Escherichia coli, Bacillus subtilis, Micrococcus leuteus and Pseudomonas aeruginosa.

Interdye Hole Transport Accelerates Recombination in Dye Sensitized Mesoporous Films.

PubMed

Moia, Davide; Szumska, Anna; Vaissier, Valérie; Planells, Miquel; Robertson, Neil; O'Regan, Brian C; Nelson, Jenny; Barnes, Piers R F

2016-10-12

Charge recombination between oxidized dyes attached to mesoporous TiO 2 and electrons in the TiO 2 was studied in inert electrolytes using transient absorption spectroscopy. Simultaneously, hole transport within the dye monolayers was monitored by transient absorption anisotropy. The rate of recombination decreased when hole transport was inhibited selectively, either by decreasing the dye surface coverage or by changing the electrolyte environment. From Monte Carlo simulations of electron and hole diffusion in a particle, modeled as a cubic structure, we identify the conditions under which hole lifetime depends on the hole diffusion coefficient for the case of normal (disorder free) diffusion. From simulations of transient absorption and transient absorption anisotropy, we find that the rate and the dispersive character of hole transport in the dye monolayer observed spectroscopically can be explained by incomplete coverage and disorder in the monolayer. We show that dispersive transport in the dye monolayer combined with inhomogeneity in the TiO 2 surface reactivity can contribute to the observed stretched electron-hole recombination dynamics and electron density dependence of hole lifetimes. Our experimental and computational analysis of lateral processes at interfaces can be applied to investigate and optimize charge transport and recombination in solar energy conversion devices using electrodes functionalized with molecular light absorbers and catalysts.

Fabrication and characterization of mixed dye: Natural and synthetic organic dye

NASA Astrophysics Data System (ADS)

Richhariya, Geetam; Kumar, Anil

2018-05-01

Mixed dye from hibiscus sabdariffa and eosin Y was employed in the fabrication of dye sensitized solar cell (DSSC). Nanostructured mesoporous film was prepared from the titanium dioxide (TiO2). The energy conversion efficiency of hibiscus, eosin Y and mixed dye was obtained as 0.41%, 1.53% and 2.02% respectively. Mixed DSSC has shown improvement in the performance of the cell as compared to hibiscus and eosin Y dye due to addition of synthetic organic dye. This illustrates the effect of synthetic organic dyes in performance enhancement of natural dyes. It has been credited to the improved absorption of light mainly in higher energy state (λ = 440-560 nm) when two dyes were employed simultaneously as was obvious from the absorption spectra of dyes adsorbed onto TiO2 electrode. The cell with TiO2 electrode sensitized by mixed dye gives short circuit current density (Jsc) = 4.01 mA/cm2, open circuit voltage (Voc) = 0.67 V, fill factor (FF) = 0.60 and energy conversion efficiency (η) of 2.02%.

Complications in complexation kinetics for lanthanides with DTPA using dye probe molecules in aqueous solution

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

Larsson, K.; Cullen, T. D.; Mezyk, S. P.

The complexation kinetics for the polyaminopolycarboxylic ligand DTPA to lanthanides in acidic aqueous solution were investigated using the dye ligand displacement technique and stopped-flow spectroscopy. Significant rate differences were obtained for different dye probes used, indicating that the kinetics of the dissociation of the dye molecule significantly impacts the overall measured kinetics when using this common methodology. The conditions of the solution also influenced the dye-lanthanide-DTPA interactions, which reconciled previously disparate data in the literature.

Complications in complexation kinetics for lanthanides with DTPA using dye probe molecules in aqueous solution

DOE PAGES

Larsson, K.; Cullen, T. D.; Mezyk, S. P.; ...

2017-05-17

The complexation kinetics for the polyaminopolycarboxylic ligand DTPA to lanthanides in acidic aqueous solution were investigated using the dye ligand displacement technique and stopped-flow spectroscopy. Significant rate differences were obtained for different dye probes used, indicating that the kinetics of the dissociation of the dye molecule significantly impacts the overall measured kinetics when using this common methodology. The conditions of the solution also influenced the dye-lanthanide-DTPA interactions, which reconciled previously disparate data in the literature.

Effect of Solvent and Substrate on the Surface Binding Mode of Carboxylate-Functionalized Aromatic Molecules

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

Domenico, Janna; Foster, Michael E.; Spoerke, Erik D.

Here, the efficiency of dye-sensitized solar cells (DSSCs) is strongly influenced by dye molecule orientation and interactions with the substrate. Understanding the factors controlling the surface orientation of sensitizing organic molecules will aid in the improvement of both traditional DSSCs and other devices that integrate molecular linkers at interfaces. Here, we describe a general approach to understand relative dye–substrate orientation and provide analytical expressions predicting orientation. We consider the effects of substrate, solvent, and protonation state on dye molecule orientation. In the absence of solvent, our model predicts that most carboxylic acid-functionalized molecules prefer to lie flat (parallel) on themore » surface, due to van der Waals interactions, as opposed to a tilted orientation with respect to the surface that is favored by covalent bonding of the carboxylic acid group to the substrate. When solvation effects are considered, however, the molecules are predicted to orient perpendicular to the surface. We extend this approach to help understand and guide the orientation of metal–organic framework (MOF) thin-film growth on various metal–oxide substrates. A two-part analytical model is developed on the basis of the results of DFT calculations and ab initio MD simulations that predicts the binding energy of a molecule by chemical and dispersion forces on rutile and anatase TiO 2 surfaces, and quantifies the dye solvation energy for two solvents. The model is in good agreement with the DFT calculations and enables rapid prediction of dye molecule and MOF linker binding preference on the basis of the size of the adsorbing molecule, identity of the surface, and the solvent environment. We establish the threshold molecular size, governing dye molecule orientation, for each condition.« less

Effect of Solvent and Substrate on the Surface Binding Mode of Carboxylate-Functionalized Aromatic Molecules

DOE PAGES

Domenico, Janna; Foster, Michael E.; Spoerke, Erik D.; ...

2018-04-25

Here, the efficiency of dye-sensitized solar cells (DSSCs) is strongly influenced by dye molecule orientation and interactions with the substrate. Understanding the factors controlling the surface orientation of sensitizing organic molecules will aid in the improvement of both traditional DSSCs and other devices that integrate molecular linkers at interfaces. Here, we describe a general approach to understand relative dye–substrate orientation and provide analytical expressions predicting orientation. We consider the effects of substrate, solvent, and protonation state on dye molecule orientation. In the absence of solvent, our model predicts that most carboxylic acid-functionalized molecules prefer to lie flat (parallel) on themore » surface, due to van der Waals interactions, as opposed to a tilted orientation with respect to the surface that is favored by covalent bonding of the carboxylic acid group to the substrate. When solvation effects are considered, however, the molecules are predicted to orient perpendicular to the surface. We extend this approach to help understand and guide the orientation of metal–organic framework (MOF) thin-film growth on various metal–oxide substrates. A two-part analytical model is developed on the basis of the results of DFT calculations and ab initio MD simulations that predicts the binding energy of a molecule by chemical and dispersion forces on rutile and anatase TiO 2 surfaces, and quantifies the dye solvation energy for two solvents. The model is in good agreement with the DFT calculations and enables rapid prediction of dye molecule and MOF linker binding preference on the basis of the size of the adsorbing molecule, identity of the surface, and the solvent environment. We establish the threshold molecular size, governing dye molecule orientation, for each condition.« less

Theory of lasing in a multiple-scattering medium

NASA Astrophysics Data System (ADS)

John, Sajeev; Pang, Gendi

1996-10-01

In several recent experiments, isotropic lasing action was observed in paints that contain rhodamine 640 dye molecules in methanol solution as gain media and titania particles as optical scatterers. These so-called paint-on laser systems are extraordinary because they are highly disordered systems. The microscopic mechanism for laser activity and the coherence properties of light emission in this multiple-light-scattering medium have not yet been elucidated. In this paper we derive the emission intensity properties of a model dye system with excited singlet and triplet electronic energy levels, which is immersed in a multiple-scattering medium with transport mean free path l*. Using physically reasonable estimates for the absorption and emission cross section for the singlet and triplet manifolds, and the singlet-triplet intersystem crossing rate, we solve the nonlinear laser rate equations for the dye molecules. This leads to a diffusion equation for the light intensity in the medium with a nonlinear intensity-dependent gain coefficient. Using this model we are able to account for nearly all of the experimentally observed properties of laser paint reported so far when l*>>λ0, the emission wavelength. This includes the dependence of the peak intensity of amplified emission on the mean free path l*, the dye concentration ρ, and the pump intensity characteristics. Our model recaptures the collapse of the emission linewidth at a specific threshold pump intensity and describes how this threshold intensity varies with l*. In addition, our model predicts a dramatic increase in the peak intensity and a further lowering of the lasing threshold for the strong scattering limit l*-->λ0. This suggests a striking enhancement of the characteristics of laser paint near the photon localization threshold in a disordered medium.

A study of the Interaction of bovine Hemoglobin with Synthetic dyes using Spectroscopic techniques and Molecular docking

NASA Astrophysics Data System (ADS)

Kamaljeet; Bansal, Saurabh; SenGupta, Uttara

2016-12-01

Synthetic dyes are a very efficient class of dyes that are ingested or come into contact with the skin from numerous sources (cosmetics, textiles, leather, paper, drugs). An important component of their safety profile is the interactions that they form after they enter the body. Hemoglobin is a functionally important protein that can form multiple interactions with soluble compounds present in the blood, and hence forms an important aspect of the toxicological or safety profile of the dyes. Here we study the interaction between bovine haemoglobin and organic dyes using UV-Vis absorbance and fluorescence spectroscopy. Molecular modelling was used to visualise the binding site and partners of the dye molecules, within the hemoglobin molecule. We find that all four dyes studied form sufficiently strong interactions with haemoglobin to allow for the formation of potentially toxic interactions. Molecular modelling showed that all 4 dyes bound within the central cavity of the haemoglobin molecule. However, binding partners could not be identified as multiple binding conformations with very similar energies were possible for each dye.

A Study of the Interaction of Bovine Hemoglobin with Synthetic Dyes Using Spectroscopic Techniques and Molecular Docking.

PubMed

Kamaljeet; Bansal, Saurabh; SenGupta, Uttara

2016-01-01

Synthetic dyes are a very efficient class of dyes that are ingested or come into contact with the skin from numerous sources (cosmetics, textiles, leather, paper, and drugs). An important component of their safety profile is the interactions that they form after they enter the body. Hemoglobin is a functionally important protein that can form multiple interactions with soluble compounds present in the blood, and hence forms an important aspect of the toxicological or safety profile of the dyes. Here we study the interaction between bovine hemoglobin and organic dyes using UV-Vis absorbance and fluorescence spectroscopy. Molecular modeling was used to visualize the binding site and partners of the dye molecules, within the hemoglobin molecule. We find that all four dyes studied form sufficiently strong interactions with hemoglobin to allow for the formation of potentially toxic interactions. Molecular modeling showed that all four dyes bind within the central cavity of the hemoglobin molecule. However, binding partners could not be identified as multiple binding conformations with very similar energies were possible for each dye.

First principles DFT study of dye-sensitized CdS quantum dots

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

Jain, Kalpna; Singh, Kh. S.; Kishor, Shyam, E-mail: shyam387@gmail.com

2014-04-24

Dye-sensitized quantum dots (QDs) are considered promising candidates for dye-sensitized solar cells. In order to maximize their efficiency, detailed theoretical studies are important. Here, we report a first principles density functional theory (DFT) investigation of experimentally realized dye - sensitized QD / ligand systems, viz., Cd{sub 16}S{sub 16}, capped with acetate molecules and a coumarin dye. The hybrid B3LYP functional and a 6−311+G(d,p)/LANL2dz basis set are used to study the geometric, energetic and electronic properties of these clusters. There is significant structural rearrangement in all the clusters studied - on the surface for the bare QD, and in the positionsmore » of the acetate / dye ligands for the ligated QDs. The density of states (DOS) of the bare QD shows states in the band gap, which disappear on surface passivation with the acetate molecules. Interestingly, in the dye-sensitised QD, the HOMO is found to be localized mainly on the dye molecule, while the LUMO is on the QD, as required for photo-induced electron injection from the dye to the QD.« less

Reversible photochromic system based on rhodamine B salicylaldehyde hydrazone metal complex.

PubMed

Li, Kai; Xiang, Yu; Wang, Xiaoyan; Li, Ji; Hu, Rongrong; Tong, Aijun; Tang, Ben Zhong

2014-01-29

Photochromic molecules are widely applied in chemistry, physics, biology, and materials science. Although a few photochromic systems have been developed before, their applications are still limited by complicated synthesis, low fatigue resistance, or incomplete light conversion. Rhodamine is a class of dyes with excellent optical properties including long-wavelength absorption, large absorption coefficient, and high photostability in its ring-open form. It is an ideal chromophore for the development of new photochromic systems. However, known photochromic rhodamine derivatives, such as amides, exhibit only millisecond lifetimes in their colored ring-open forms, making their application very limited and difficult. In this work, rhodamine B salicylaldehyde hydrazone metal complex was found to undergo intramolecular ring-open reactions upon UV irradiation, which led to a distinct color and fluorescence change both in solution and in solid matrix. The complex showed good fatigue resistance for the reversible photochromism and long lifetime for the ring-open state. Interestingly, the thermal bleaching rate was tunable by using different metal ions, temperatures, solvents, and chemical substitutions. It was proposed that UV light promoted isomerization of the rhodamine B derivative from enol-form to keto-form, which induced ring-opening of the rhodamine spirolactam in the complex to generate color. The photochromic system was successfully applied for photoprinting and UV strength measurement in the solid state. As compared to other reported photochromic molecules, the system in this study has its advantages of facile synthesis and tunable thermal bleaching rate, and also provides new insights into the development of photochromic materials based on metal complex and spirolactam-containing dyes.

Time-Delayed Two-Step Selective Laser Photodamage of Dye-Biomolecule Complexes

NASA Astrophysics Data System (ADS)

Andreoni, A.; Cubeddu, R.; de Silvestri, S.; Laporta, P.; Svelto, O.

1980-08-01

A scheme is proposed for laser-selective photodamage of biological molecules, based on time-delayed two-step photoionization of a dye molecule bound to the biomolecule. The validity of the scheme is experimentally demonstrated in the case of the dye Proflavine, bound to synthetic polynucleotides.

Complexation induced fluorescence and acid-base properties of dapoxyl dye with γ-cyclodextrin: a drug-binding application using displacement assays.

PubMed

Pal, Kaushik; Mallick, Suman; Koner, Apurba L

2015-06-28

Host-guest complexation of dapoxyl sodium sulphonate (DSS), an intramolecular charge transfer dye with water-soluble and non-toxic macrocycle γ-cyclodextrin (γ-CD), has been investigated in a wide pH range. Steady-state absorption, fluorescence and time-resolved fluorescence measurements confirm the positioning of DSS into the hydrophobic cavity of γ-CD. A large fluorescence enhancement ca. 30 times, due to 1 : 2 complex formation and host-assisted guest-protonation have been utilised for developing a method for the utilisation of CD based drug-delivery applications. A simple fluorescence-displacement based approach is implemented at physiological pH for the assessment of binding strength of pharmaceutically useful small drug molecules (ibuprofen, paracetamol, methyl salicylate, salicylic acid, aspirin, and piroxicam) and six important antibiotic drugs (resazurin, thiamphenicol, chloramphenicol, ampicillin, kanamycin, and sorbic acid) with γ-CD.

Third-order nonlinear optical properties of acid green 25 dye by Z-scan method

NASA Astrophysics Data System (ADS)

Jeyaram, S.; Geethakrishnan, T.

2017-03-01

Third-order nonlinear optical (NLO) properties of aqueous solutions of an anthraquinone dye (Acid green 25 dye, color index: 61570) have been studied by Z-scan method with a 5 mW continuous wave (CW) diode laser operating at 635 nm. The nonlinear refractive index (n2) and the absorption coefficient (β) have been evaluated respectively from the closed and open aperture Z-scan data and the values of these parameters are found to increase with increase in concentration of the dye solution. The negative sign of the observed nonlinear refractive index (n2) indicates that the aqueous solution of acid green 25 dye exhibits self-defocusing type optical nonlinearity. The mechanism of the observed nonlinear absorption (NLA) and nonlinear refraction (NLR) is attributed respectively to reverse saturable absorption (RSA) and thermal nonlinear effects. The magnitudes of n2 and β are found to be of the order of 10-7 cm2/W and 10-3 cm/W respectively. With these experimental results, the authors suggest that acid green 25 dye may have potential applications in nonlinear optics.

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.

Mediterranean Workshop and Topical Meeting. Novel Optical Materials and Applications NOMA 󈧅 (5th) Held in Cetraro (Italy) on May 20-26, 2001

DTIC Science & Technology

2002-09-12

low power dissipation, and low cost. Excited state absorption and reorientation in polymethine and squarylium dyes . David J. Hagana, Olga V...describe a detailed theoretical and experimental study of the excited states of polymethine and squarylium dyes . Picosecond, polarization-resolved...transient absorption and anisotropy excitation measurements were performed in several polymethine and squarylium dyes in ethanol solutions and

Optical properties of thin merocyanine dye layers for photovoltaic applications

NASA Astrophysics Data System (ADS)

Dikova, J.; Kitova, S.; Stoyanova, D.; Vasilev, A.; Deligeorgiev, T.; Angelova, S.

2014-05-01

The potentiality was studied of our newly synthesized push-pull type merocyanine dye, labeled A1, for use as an electron donating component in solution-processed bulk heterojunction (BHJ) organic solar cells. For the purpose, a soluble n-type fullerene, (6,6)-phenyl C61 butyric acid methyl ester (PCBM), which is currently and in the ear future without an alternative, was chosen as an acceptor. The optical constants (n and k) of thin films obtained by spin coating from solutions in chlorobenzene of A1 and of an A1/PCBM blend were determined by spectrophotometric measurements. Further, an optical simulation of a standard BHJ cell with an active layer of an A1dye/PCMB blend was performed using a transfer-matrix formalism. Thus, the optimum thickness of the active layer was calculated to be about 80 nm, which provides overlapping of the total absorption with the solar spectrum in the broad range 400 nm - 800 nm. Finally, the maximum current density, Jsc, was determined to be 13 mA cm2 assuming that the internal quantum efficiency, IQE, is unity. Comparing the calculated Jsc with data on some advanced small-molecule BHJ devices, the prospects for practical applications of the new merocyanine dye are discussed.

Characteristics of color optical shutter with dye-doped polymer network liquid crystal.

PubMed

Lee, G H; Hwang, K Y; Jang, J E; Jin, Y W; Lee, S Y; Jung, J E

2011-03-01

The optical properties and the theoretical prediction of color optical shutter with dye-doped polymer network liquid crystal (PNLC) were investigated. The view-angle dependence of reflectance according to the bias conditions showed distinctive characteristics, which could be explained from the effects of dye absorption and path length. It was also shown that the thickness dependence of reflectance was strongly influenced by the light-scattering coefficient. Our experimental results matched up well with the theoretical prediction based on the light scattering of liquid crystals in polymer network and the absorption of dichroic dye. This work indicates potential to improve the optical device using dye-doped liquid crystal-polymer composite.

Temperature effect of natural organic extraction upon light absorbance in dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Suhaimi, Suriati; Mohamed Siddick, Siti Zubaidah; Retnasamy, Vithyacharan; Abdul Wahid, Mohamad Halim; Ahmad Hambali, Nor Azura Malini; Mohamad Shahimin, Mukhzeer

2017-02-01

Natural organic dyes contain pigments which when safely extracted from plants have the potential to be used as a sensitizer while promising a low-cost fabrication, environmental friendly dye-sensitized solar cells (DSSCs). Ardisia, Bawang Sabrang, Harum Manis mango, Oxalis Triangularis and Rosella showed different absorption peaks when the extraction process were carried out at different temperatures. Hence, these were used as the basis to determine the conversion efficiency against the dyes extracting temperature. In this study, all dyes extracted in water have shown the best performance at a temperature of 100°C except for Harum Manis mango, while in ethanol, the optimum temperature was obtained between the room temperature, 25°C and 50°C. The absorption spectrum in water showed a broader absorption wavelength vis-à-vis ethanol solvent that resulted in the absorption peak for Ardisia, Harum Manis mango and Rosella between 450 nm and 550 nm. The highest conversion efficiency is observed to be achieved by Oxalis Triangularis extracted in water solution at 100°C, which was approximately 0.96% which corresponds to the broader absorbance trends in the literature. Thus, the optimum condition for extracting temperature for dyes in water and ethanol is room temperature and boiling points of water. Hence, Ardisia, Bawang Sabrang, Harum Manis mango, Oxalis Triangularis and Rosella can be an as alternative source for photosensitizer, and the impacts of temperature upon the light absorbance can be further investigated to produce the ultimate natural dye based solar cells.

Multispectral Photoacoustic Imaging of Tumor Protease Activity with a Gold Nanocage-Based Activatable Probe.

PubMed

Liu, Cheng; Li, Shiying; Gu, Yanjuan; Xiong, Huahua; Wong, Wing-Tak; Sun, Lei

2018-05-07

Tumor proteases have been recognized as significant regulators in the tumor microenvironment, but the current strategies for in vivo protease imaging have tended to focus on the development of a probe design rather than the investigation of a novel imaging strategy by leveraging the imaging technique and probe. Herein, it is the first report to investigate the ability of multispectral photoacoustic imaging (PAI) to estimate the distribution of protease cleavage sites inside living tumor tissue by using an activatable photoacoustic (PA) probe. The protease MMP-2 is selected as the target. In this probe, gold nanocages (GNCs) with an absorption peak at ~ 800 nm and fluorescent dye molecules with an absorption peak at ~ 680 nm are conjugated via a specific enzymatic peptide substrate. Upon enzymatic activation by MMP-2, the peptide substrate is cleaved and the chromophores are released. Due to the different retention speeds of large GNCs and small dye molecules, the probe alters its intrinsic absorption profile and produces a distinct change in the PA signal. A multispectral PAI technique that can distinguish different chromophores based on intrinsic PA spectral signatures is applied to estimate the signal composition changes and indicate the cleavage interaction sites. Finally, the multispectral PAI technique with the activatable probe is tested in solution, cultured cells, and a subcutaneous tumor model in vivo. Our experiment in solution with enzyme ± inhibitor, cell culture ± inhibitor, and in vivo tumor model with administration of the developed probe ± inhibitor demonstrated the probe was cleaved by the targeted enzyme. Particularly, the in vivo estimation of the cleavage site distribution was validated with the result of ex vivo immunohistochemistry analysis. This novel synergy of the multispectral PAI technique and the activatable probe is a potential strategy for the distribution estimation of tumor protease activity in vivo.

Dye-Sensitized Approaches to Photovoltaics

NASA Astrophysics Data System (ADS)

Grätzel, Michael

2008-03-01

Sensitization of wide band-gap semiconductors to photons of energy less than the band-gap is a key step in two technically important processes - panchromatic photography and photoelectrochemical solar cells. In both cases the photosensitive species is not the semiconductor - silver halide or metal oxide - but rather an electrochemically active dye. The gap between the highest occupied molecular level (HOMO) and the lowest unoccupied molecular level (LUMO) is less than the band-gap of the semiconductor with which it is associated. It can therefore absorb light of a wavelength longer than that to which the semiconductor itself is sensitive. The electrochemical process is initiated when the dye molecule relaxes from its photoexcited level by electron injection into the semiconductor, which therefore acts as a photoanode. If the dye is in contact with a redox electrolyte, the negative charge represented by the lost electron can be recovered from the reduced state of the redox system, which in return is regenerated by charge transfer from a cathode. An external load completes the electrical circuit. The system therefore represents a conversion of the energy of absorbed photons into an electrical current by a regenerative device in every functional respect analogous to a solid-state photovoltaic cell. As in any engineering system, choice of materials, their optimization and their synergy are essential to efficient operation. While a semiconductor-electrolyte contact is analogous to a Schottky contact, in that a barrier is established between two materials of different conduction mechanism, with the possibility of optical absorption, charge carrier pair generation and separation, it should be remembered that the photogenerated valence band hole in the semiconductor represents a powerful oxidizing agent. Given that the band-gap is related to the strength and therefore the stability of chemical bonding within the semiconductor, for narrow-gap materials the most likely reaction of such a hole is the photocorrosion of the semiconductor itself. However, only relatively narrow band-gap materials have an effective optical absorption through the visible spectrum, towards and into the infra-red. Materials with an optimal band-gap match to the solar spectrum, of the order of 1.5eV, are therefore electrochemically unstable. A stable photoelectrochemical cell, without some process of optical sensitization, and necessarily using a wide-gap semiconductor is sensitive only to the ultra-violet limit of the visible spectrum. Over recent years a suitable combination of semiconductor and sensitizer has been identified and optimized, so that now a solar spectrum conversion efficiency of over 11% has been verified in a sensitized photoelectrochemical device. One key to such an efficient system is the suppression of recombination losses. When the excited dye relaxes by electron loss, the separated charge carriers find themselves on opposite sides of a phase barrier -- the electron within the solid-state semiconductor, the positive charge externally, in association with the dye molecule. There is no valence---band involvement in the process, so the system represents a majority-carrier device, avoiding one of the major loss mechanisms in conventional photovoltaics. In consequence also a highly-disordered, even porous, semiconductor structure is acceptable, enabling surface adsorption of a sufficient concentration of the dye to permit total optical absorption of incident light of photon energy greater than the HOMO-LUMO gap of the dye molecule. The accepted wide-band semiconductor for photoelectrochemical applications is titanium dioxide in the anatase crystal structure. The size of the nanocrystals making up the semiconductor photoanode can be determined by hydrothermal processing of a precursor sol, and the film can be deposited on a transparent conducting oxide (TCO) substrate by any convenient thin-film process such as screen printing or tape casting. The preferred dye system is inspired by the natural processes involving chlorophyll, the coloring material in plants on which all earthly life depends. Chlorophyll is an organometallic dye, with a metal ion, Mg, within a porphyrin cage of nitrogen atoms. The synthetic chemist of course can select any convenient metal within the periodic table, and experience shows that ruthenium has the optimal properties expected. A ruthenium-pyridyl complex provides the chromophore of the dye, with the HOMO-LUMO gap, and thence the absorption spectrum bring modified by substitution with thiocyanide groups. Chemisorptive attachment of the dye to the metal oxide surface is obtained by carboxyl groups attached to the pyridyl components. The energetics of the dye is such that the LUMO level is just above the conduction band edge of the semiconductor, enabling relaxation by electron injection as required. A satisfactory electroactive dye structure, with good attachment properties and a wide optical absorption spectrum is therefore a sophisticated molecular engineering product. The electrolyte is also an optimized electrochemical system. The basic redox behavior is provided by the iodine/iodide system, with the advantage that the ions, both oxidized and reduced are relatively small, and therefore mobile in the supporting electrolyte. Energy losses due to slow diffusion are minimized. Early experiments used aqueous electrolytes, though with limited cell lifetime due to hydrolysis of the chemisorptive dye---semiconductor bond. A wide range of organic systems were therefore investigated, with the present favored formulation being based on imidazole salts. These have the additional advantage of low vapor pressure, very necessary as the photoactive sites under mid---day sun illumination may reach 80 C or higher. Low losses at the cathode counterelectrode are also a requirement for cell efficiency. The cathode is not necessarily transparent, and prototype cells on thin metal foils have been produced. However a TCO on glass or polymer counterelectrode is widely used. In either case suitable electrocatalytic behavior is required and frequently a nanodispersed Pt precipitated from haxachloride solution is employed. It is by now evident that the achievement of an industrially-competitive sensitized photoelectrochemical solar cell is the result of the optimization of several components, associated obviously with their effective synergy. Each change of a single component has repercussions on the choice and performance of others. However as already mentioned an efficiency of over 11% has now been certified, and a stability of over 14,000 hours under accelerated testing with continuous simulated AM1.5 illumination was recently reported. In consequence there is increasing confidence on the part of industry. Several licensees of EPFL patents on dye---sensitized photovoltaic systems are now preparing for large-scale production. G24 Innovations PLC in Wales is commissioning a manufacturing plant, and Dyesol PLC in Australia is making available the required materials on an industrial scale. In conclusion, then, it can be stated that the DSC system is much more than a fascinating scientific artifact illustrating charge-transfer mechanisms at electrochemical interfaces; an efficiency and reliability with industrial credibility have been demonstrated and verified, and a significant role in competition with other photosystems can be foreseen.

Photoactive dye enhanced tissue ablation for endoscopic laser prostatectomy

NASA Astrophysics Data System (ADS)

Ahn, Minwoo; Nguyen, Trung Hau; Nguyen, Van Phuc; Oh, Junghwan; Kang, Hyun Wook

2015-02-01

Laser light has been widely used as a surgical tool to treat benign prostate hyperplasia with high laser power. The purpose of this study was to validate the feasibility of photoactive dye injection to enhance light absorption and eventually to facilitate tissue ablation with low laser power. The experiment was implemented on chicken breast due to minimal optical absorption Amaranth (AR), black dye (BD), hemoglobin powder (HP), and endoscopic marker (EM), were selected and tested in vitro with a customized 532-nm laser system with radiant exposure ranging from 0.9 to 3.9 J/cm2. Light absorbance and ablation threshold were measured with UV-VIS spectrometer and Probit analysis, respectively, and compared to feature the function of the injected dyes. Ablation performance with dye-injection was evaluated in light of radiant exposure, dye concentration, and number of injection. Higher light absorption by injected dyes led to lower ablation threshold as well as more efficient tissue removal in the order of AR, BD, HP, and EM. Regardless of the injected dyes, ablation efficiency principally increased with input parameter. Among the dyes, AR created the highest ablation rate of 44.2+/-0.2 μm/pulse due to higher absorbance and lower ablation threshold. Preliminary tests on canine prostate with a hydraulic injection system demonstrated that 80 W with dye injection yielded comparable ablation efficiency to 120 W with no injection, indicating 33 % reduced laser power with almost equivalent performance. In-depth comprehension on photoactive dye-enhanced tissue ablation can help accomplish efficient and safe laser treatment for BPH with low power application.

SISGR: Room Temperature Single-Molecule Detection and Imaging by Stimulated Emission Microscopy

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

Xie, Xiaoliang Sunney

Single-molecule spectroscopy has made considerable impact on many disciplines including chemistry, physics, and biology. To date, most single-molecule spectroscopy work is accomplished by detecting fluorescence. On the other hand, many naturally occurring chromophores, such as retinal, hemoglobin and cytochromes, do not have detectable fluorescence. There is an emerging need for single-molecule spectroscopy techniques that do not require fluorescence. In the last proposal period, we have successfully demonstrated stimulated emission microscopy, single molecule absorption, and stimulated Raman microscopy based on a high-frequency modulation transfer technique. These first-of-a- kind new spectroscopy/microscopy methods tremendously improved our ability to observe molecules that fluorescence weakly,more » even to the limit of single molecule detection for absorption measurement. All of these methods employ two laser beams: one (pump beam) excites a single molecule to a real or virtual excited state, and the other (probe beam) monitors the absorption/emission property of the single. We extract the intensity change of the probe beam with high sensitivity by implementing a high-frequency phase-sensitive detection scheme, which offers orders of magnitude improvement in detection sensitivity over direct absorption/emission measurement. However, single molecule detection based on fluorescence or absorption is fundamentally limited due to their broad spectral response. It is important to explore other avenues in single molecule detection and imaging which provides higher molecular specificity for studying a wide variety of heterogeneous chemical and biological systems. This proposal aimed to achieve single-molecule detection sensitivity with near resonance stimulated Raman scattering (SRS) microscopy. SRS microscopy was developed in our lab as a powerful technique for imaging heterogeneous samples based on their intrinsic vibrational contrasts, which provides much higher molecular specificity than absorption and fluorescence. Current sensitivity limit of SRS microscopy has not yet reached single molecule detection. We proposed to capitalize on our state-of-the-art SRS microscopy and develop near-resonance enhanced SRS for single molecule detection of carotenoids and heme proteins. The specific aims we pursued are: (1) building the next SRS generation microscope that utilizes near resonance enhancement to allow detection and imaging of single molecules with undetectable fluorescence, such as -carotene. (2) using near-resonance SRS as a contrast mechanism to study dye-sensitize semiconductor interface, elucidating the heterogeneous electron ejection kinetics with high spatial and temporal resolution. (3) studying the binding and unbinding of oxygen in single hemoglobin molecules in order to gain molecular level understanding of the long-standing issue of cooperativity. The new methods developed in the fund period of this grant have advanced the detection sensitivity in many aspects. Near-resonance SRS improved the signal by using shorter wavelengths for SRS microscopy. Frequency modulation and multi-color SRS target the reduction of background to improve the chemical specificity of SRS while maintaining the high imaging speed. Time-domain coherent Raman scattering microscopy targets to reduce the noise floor of coherent Raman microscopy. These methods have already demonstrated first-of-a-kind new applications in biology and medical research. However, we are still one order of magnitude away from single molecule limit. It is important to continue to improve the laser specification and develop new imaging methods to finally achieve label-free single molecule microscopy.« less

Improved Dye Stability in Single-Molecule Fluorescence Experiments

NASA Astrophysics Data System (ADS)

EcheverrÍa Aitken, Colin; Marshall, R. Andrew; Pugi, Joseph D.

Complex biological systems challenge existing single-molecule methods. In particular, dye stability limits observation time in singlemolecule fluorescence applications. Current approaches to improving dye performance involve the addition of enzymatic oxygen scavenging systems and small molecule additives. We present an enzymatic oxygen scavenging system that improves dye stability in single-molecule experiments. Compared to the currently-employed glucose-oxidase/catalase system, the protocatechuate-3,4-dioxygenase system achieves lower dissolved oxygen concentration and stabilizes single Cy3, Cy5, and Alexa488 fluorophores. Moreover, this system possesses none of the limitations associated with the glucose oxidase/catalase system. We also tested the effects of small molecule additives in this system. Biological reducing agents significantly destabilize the Cy5 fluorophore as a function of reducing potential. In contrast, anti-oxidants stabilize the Cy3 and Alexa488 fluorophores. We recommend use of the protocatechuate-3,4,-dioxygenase system with antioxidant additives, and in the absence of biological reducing agents. This system should have wide application to single-molecule fluorescence experiments.

Self-healing of optical functions by molecular metabolism in a swollen elastomer

NASA Astrophysics Data System (ADS)

Saito, Mitsunori; Nishimura, Tatsuya; Sakiyama, Kohei; Inagaki, Sota

2012-12-01

Optical functions of organic dyes, e.g., fluorescence or photochromism, tend to degrade by light irradiation, which causes a short lifetime of photonic devices. Self-healing of optical functions is attainable by metabolizing bleached molecules with nonirradiated ones. A polydimethylsiloxane elastomer provides a useful matrix for dye molecules, since its flexible structure with nano-sized intermolecular spaces allows dye diffusion from a reservoir to an operation region. Swelling the elastomer with a suitable solvent promotes both dissolution and diffusion of dye molecules. This self-healing function was demonstrated by an experiment in which a photochromic elastomer exhibited improved durability against a repeated coloring-decoloring process.

Hydrophobic fluorescent probes introduce artifacts into single molecule tracking experiments due to non-specific binding.

PubMed

Zanetti-Domingues, Laura C; Tynan, Christopher J; Rolfe, Daniel J; Clarke, David T; Martin-Fernandez, Marisa

2013-01-01

Single-molecule techniques are powerful tools to investigate the structure and dynamics of macromolecular complexes; however, data quality can suffer because of weak specific signal, background noise and dye bleaching and blinking. It is less well-known, but equally important, that non-specific binding of probe to substrates results in a large number of immobile fluorescent molecules, introducing significant artifacts in live cell experiments. Following from our previous work in which we investigated glass coating substrates and demonstrated that the main contribution to this non-specific probe adhesion comes from the dye, we carried out a systematic investigation of how different dye chemistries influence the behaviour of spectrally similar fluorescent probes. Single-molecule brightness, bleaching and probe mobility on the surface of live breast cancer cells cultured on a non-adhesive substrate were assessed for anti-EGFR affibody conjugates with 14 different dyes from 5 different manufacturers, belonging to 3 spectrally homogeneous bands (491 nm, 561 nm and 638 nm laser lines excitation). Our results indicate that, as well as influencing their photophysical properties, dye chemistry has a strong influence on the propensity of dye-protein conjugates to adhere non-specifically to the substrate. In particular, hydrophobicity has a strong influence on interactions with the substrate, with hydrophobic dyes showing much greater levels of binding. Crucially, high levels of non-specific substrate binding result in calculated diffusion coefficients significantly lower than the true values. We conclude that the physic-chemical properties of the dyes should be considered carefully when planning single-molecule experiments. Favourable dye characteristics such as photostability and brightness can be offset by the propensity of a conjugate for non-specific adhesion.

Hydrophobic Fluorescent Probes Introduce Artifacts into Single Molecule Tracking Experiments Due to Non-Specific Binding

PubMed Central

Rolfe, Daniel J.; Clarke, David T.; Martin-Fernandez, Marisa

2013-01-01

Single-molecule techniques are powerful tools to investigate the structure and dynamics of macromolecular complexes; however, data quality can suffer because of weak specific signal, background noise and dye bleaching and blinking. It is less well-known, but equally important, that non-specific binding of probe to substrates results in a large number of immobile fluorescent molecules, introducing significant artifacts in live cell experiments. Following from our previous work in which we investigated glass coating substrates and demonstrated that the main contribution to this non-specific probe adhesion comes from the dye, we carried out a systematic investigation of how different dye chemistries influence the behaviour of spectrally similar fluorescent probes. Single-molecule brightness, bleaching and probe mobility on the surface of live breast cancer cells cultured on a non-adhesive substrate were assessed for anti-EGFR affibody conjugates with 14 different dyes from 5 different manufacturers, belonging to 3 spectrally homogeneous bands (491 nm, 561 nm and 638 nm laser lines excitation). Our results indicate that, as well as influencing their photophysical properties, dye chemistry has a strong influence on the propensity of dye-protein conjugates to adhere non-specifically to the substrate. In particular, hydrophobicity has a strong influence on interactions with the substrate, with hydrophobic dyes showing much greater levels of binding. Crucially, high levels of non-specific substrate binding result in calculated diffusion coefficients significantly lower than the true values. We conclude that the physic-chemical properties of the dyes should be considered carefully when planning single-molecule experiments. Favourable dye characteristics such as photostability and brightness can be offset by the propensity of a conjugate for non-specific adhesion. PMID:24066121

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Influence of the layer thickness and concentration of dye molecules on the emission amplification in cholesteric liquid crystals

NASA Astrophysics Data System (ADS)

Alaverdyan, R. B.; Gevorgyan, A. A.; Chilingaryan, A. D.; Chilingaryan, Yu S.

2008-05-01

The propagation of light through a planar layer of a cholesteric liquid crystal doped with dye molecules is considered. The features of the emission spectra of the crystal are studied both in the absence and presence of dielectric boundaries. The increase in the emission intensity is investigated for different layer thicknesses and different concentrations of dye molecules. It is shown that an anomalously strong increase in the emission intensity with the diffraction intrinsic polarisation takes place in the case of a comparatively small crystal thickness and a relatively low concentration of dye molecules. The obtained results can be used for the development of miniature lasers with the circular polarisation of the fundamental radiation mode.

Single molecule studies of solvent-dependent diffusion and entrapment in poly(dimethylsiloxane) thin films.

PubMed

Lange, Jeffrey J; Culbertson, Christopher T; Higgins, Daniel A

2008-12-15

Single molecule microscopic and spectroscopic methods are employed to probe the mobility and physical entrapment of dye molecules in dry and solvent-loaded poly(dimethylsiloxane) (PDMS) films. PDMS films of approximately 220 nm thickness are prepared by spin casting dilute solutions of Sylgard 184 onto glass coverslips, followed by low temperature curing. A perylene diimide dye (BPPDI) is used to probe diffusion and molecule-matrix interactions. Two classes of dye-loaded samples are investigated: (i) those incorporating dye dispersed throughout the films ("in film" samples) and (ii) those in which the dye is restricted primarily to the PDMS surface ("on film" samples). Experiments are performed under dry nitrogen and at various levels of isopropyl alcohol (IPA) loading from the vapor phase. A PDMS-coated quartz-crystal microbalance is employed to monitor solvent loading and drying of the PDMS and to ensure equilibrium conditions are achieved. Single molecules are shown to be predominantly immobile under dry conditions and mostly mobile under IPA-saturated conditions. Quantitative methods for counting the fluorescent spots produced by immobile single molecules in optical images of the samples demonstrate that the population of mobile molecules increases nonlinearly with IPA loading. Even under IPA saturated conditions, the population of fixed molecules is found to be greater than zero and is greatest for "in film" samples. Fluorescence correlation spectroscopy is used to measure the apparent diffusion coefficient for the mobile molecules, yielding a mean value of D = 1.4(+/-0.4) x 10(-8) cm(2)/s that is virtually independent of IPA loading and sample class. It is concluded that a nonzero population of dye molecules is physically entrapped within the PDMS matrix under all conditions. The increase in the population of mobile molecules under high IPA conditions is attributed to the filling of film micropores with solvent, rather than by incorporation of molecularly dispersed solvent into the PDMS.

Studies on the optical and photoelectric properties of anthocyanin and chlorophyll as natural co-sensitizers in dye sensitized solar cell

NASA Astrophysics Data System (ADS)

Nan, Hui; Shen, He-Ping; Wang, Gang; Xie, Shou-Dong; Yang, Gui-Jun; Lin, Hong

2017-11-01

Anthocyanin and Chlorophyll extracted from Troll flower and Cypress leaf respectively are used as natural sensitizers in dye sensitized solar cells (DSCs), with their optical and electrochemical properties investigated. UV-Vis absorption measurement showed that the mixture of two dyes enabled an enhanced and wider absorption in the wavelength range of 300 nm-700 nm compared to each single dye. FTIR results proved that anthocyanin is chemically adsorbed onto the TiO2 film, while it is physical adsorption for chlorophyll. The energy level offsets on the TiO2/dye/electrolyte interface for each dye and the dye mixture with different ratios were calculated from the electrochemical analysis, which affect the electron injection and dye regeneration efficiencies. The optimized ratio of the two dyes in the mixture was found to be ∼2:5, inducing both sufficient charge transfer driving force and minimal energy loss. By incorporating this mixture into the solar cell as co-adsorbing sensitizer, the photovoltaic performance was prominently improved compared with the single dye sensitization system.

Feasibility of using RH795 dye for photoacoustic imaging of neuro-electrical activity

NASA Astrophysics Data System (ADS)

Rasheed, Nashaat; Cressman, John R.; Chitnis, Parag V.

2017-02-01

Currently, the most researched noninvasive approach for monitoring neuro-electrical activity involves opticalfluorescence imaging, which suffers from limited imaging penetration. We propose an alternative approach, photoacoustic imaging (PAI) of biopotentials, that relies on transient absorption of light by voltage-sensitive probes and subsequent generation/detection of ultrasound. PAI-based voltage imaging approach can offer the same advantages as the fluorescence imaging in terms of sensitivity and molecular specificity, but it also can significantly extend the imaging depth. In this pilot study we are investigating the feasibility of photoacoustically visualizing biopotentials in rat pheochromocytoma (PC12) cells tagged with voltage-sensitive styrylpyridinium dye, RH795. A change in the intramembrane potential was induced in PC12 cells by adding tetraphenylborate (TPB) to the cell culture. A custommade absorption spectrophotometer was used to verify the change in optical absorption of RH795 dye as a result of TPBinduced electrical fields. Absorption spectra recorded before and after the addition of 100 μM TPB exhibited a wavelength shift of the absorption peak (approximately 510 nm to 550 nm) as well as an increase in the overall magnitude of absorption in the wavelength range of 500-1000 nm. The absorption spectral measurements indicated that RH795 is a good candidate as a voltage-sensitive dye for photoacoustically tracking changes in cell-membrane potential.

A DNA Crystal Designed to Contain Two Molecules per Asymmetric Unit

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

T Wang; R Sha; J Birktoft

2011-12-31

We describe the self-assembly of a DNA crystal that contains two tensegrity triangle molecules per asymmetric unit. We have used X-ray crystallography to determine its crystal structure. In addition, we have demonstrated control over the colors of the crystals by attaching either Cy3 dye (pink) or Cy5 dye (blue-green) to the components of the crystal, yielding crystals of corresponding colors. Attaching the pair of dyes to the pair of molecules yields a purple crystal.

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1998-01-01

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution.

Sensitization of photoprocesses in colloidal Ag2S quantum dots by dye molecules

NASA Astrophysics Data System (ADS)

Ovchinnikov, Oleg V.; Kondratenko, Tamara S.; Grevtseva, Irina G.; Smirnov, Mikhail S.; Pokutnyi, Sergey I.

2016-07-01

The effect of photosensitization of IR luminescence excitation (1205 nm) of colloidal Ag2S quantum dots (QDs) with average size of 2.5±0.6 nm in gelatin at 600 to 660 nm by molecules of 3,3'-di-(γ-sulfopropyl)-4,4',5,5'-dibenzo-9-ethylthiacarbocyanine betaine pyridinium salt (Dye1) and thionine dye (Dye2) was registered. Cis-J-aggregates of Dye1 and cations monomer of Dye2 conjugated with Ag2S QDs take part in this process. The photosensitization of luminescence excitation of colloidal Ag2S QDs was interpreted by resonance nonradiation transfer of electronic excitation energy from cis-J-aggregates of Dye1 and cations of Dye2 to centers of recombination luminescence of Ag2S QDs.

Investigation of the influence of coadsorbent dye upon the interfacial structure of dye-sensitized solar cells

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

Honda, M., E-mail: honda.mitsunori@jaea.go.jp; Miyano, K.; Yanagida, M.

2014-11-07

The interface between Ru(tcterpy)(NCS){sub 3}TBA{sub 2} [black dye (BD); tcterpy = 4,4{sup ′},4{sup ″}-tricarboxy-2,2{sup ′}:6{sup ′},2{sup ″}-terpyridine, NCS = thiocyanato, TBA = tetrabutylammonium cation] and nanocrystalline TiO{sub 2}, as found in dye-sensitized solar cells, is investigated by soft-X-ray synchrotron radiation and compared with the adsorption structure of cis-Ru(Hdcbpy){sub 2}(NCS){sub 2}TBA{sub 2} (N719; dcbpy = 4,4{sup ′}-dicarboxy-2,2{sup ′}-bipyridine) on TiO{sub 2} to elucidate the relationship between the adsorption mode of BD and the photocurrent with and without coadsorbed indoline dye D131. The depth profile is characterized with X-ray photoelectron spectroscopy and S K-edge X-ray absorption fine structure using synchrotron radiation. Bothmore » datasets indicate that one of the isothiocyanate groups of BD interacts with TiO{sub 2} via its S atom when the dye is adsorbed from a single-component solution. In contrast, the interaction is slightly suppressed when D131 is coadsorbed, indicated by the fact that the presence of D131 changes the adsorption mode of BD. Based upon these results, the number of BD dye molecules interacting with the substrate is shown to decrease by 10% when D131 is coadsorbed, and the dissociation is shown to be related to the short-circuit photocurrent in the 600–800 nm region. The design of a procedure to promote the preferential adsorption of D131 therefore leads to an improvement of the short-circuit current and conversion efficiency.« less

Near-infrared dyes for molecular probes and imaging

NASA Astrophysics Data System (ADS)

Patonay, Gabor; Beckford, Garfield; Strekowski, Lucjan; Henary, Maged; Kim, Jun Seok; Crow, Sidney

2009-02-01

Near-Infrared (NIR) fluorescence has been used both as an analytical tool as molecular probes and in in vitro or in vivo imaging of individual cells and organs. The NIR region (700-1100 nm) is ideal with regard to these applications due to the inherently lower background interference and the high molar absorptivities of NIR chromophores. NIR dyes are also useful in studying binding characteristics of large biomolecules, such as proteins. Throughout these studies, different NIR dyes have been evaluated to determine factors that control binding to biomolecules, including serum albumins. Hydrophobic character of NIR dyes were increased by introducing alkyl and aryl groups, and hydrophilic moieties e.g., polyethylene glycols (PEG) were used to increase aqueous solubility. Recently, our research group introduced bis-cyanines as innovative NIR probes. Depending on their microenvironment, bis-cyanines can exist as an intramolecular dimer with the two cyanines either in a stacked form, or in a linear conformation in which the two subunits do not interact with each other. In this intramolecular H-aggregate, the chromophore has a low extinction coefficient and low fluorescence quantum yield. Upon addition of biomolecules, the H-and D- bands are decreased and the monomeric band is increased, with concomitant increase in fluorescence intensity. Introduction of specific moieties into the NIR dye molecules allows for the development of physiological molecular probes to detect pH, metal ions and other parameters. Examples of these applications include imaging and biomolecule characterizations. Water soluble dyes are expected to be excellent candidates for both in vitro and in vivo imaging of cells and organs.

Polarization dependent two-photon absorption spectroscopy on a naturally occurring biomarker (curcumin) in solution: A theoretical-experimental study

NASA Astrophysics Data System (ADS)

Tiburcio-Moreno, Jose A.; Alvarado-Gil, J. J.; Diaz, Carlos; Echevarria, Lorenzo; Hernández, Florencio E.

2013-09-01

We report on the theoretical-experimental analysis of the two-photon absorption (TPA) and two-photon circular-linear dichroism (TPCLD) spectra of (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione (curcumin) in Tetrahydrofuran (THF) solution. The measurement of the full TPA spectrum of this molecule reveals a maximum TPA cross-section at 740 nm, i.e. more than 10 times larger than the maximum reported in the literature at 800 nm for the application of curcumin in bioimaging. The TPCLD spectrum exposes the symmetry of the main excited-states involved in the two-photon excitation process. TD-DFT calculations support the experimental results. These outcomes are expected to expand the application of natural-occurring dyes in bioimaging.

Absorption into fluorescence. A method to sense biologically relevant gas molecules

NASA Astrophysics Data System (ADS)

Strianese, Maria; Varriale, Antonio; Staiano, Maria; Pellecchia, Claudio; D'Auria, Sabato

2011-01-01

In this work we present an innovative optical sensing methodology based on the use of biomolecules as molecular gating nano-systems. Here, as an example, we report on the detection ofanalytes related to climate change. In particular, we focused our attention on the detection ofnitric oxide (NO) and oxygen (O2). Our methodology builds on the possibility of modulating the excitation intensity of a fluorescent probe used as a transducer and a sensor molecule whose absorption is strongly affected by the binding of an analyte of interest used as a filter. The two simple conditions that have to be fulfilled for the method to work are: (a) the absorption spectrum of the sensor placed inside the cuvette, and acting as the recognition element for the analyte of interest, should strongly change upon the binding of the analyte and (b) the fluorescence dye transducer should exhibit an excitation band which overlaps with one or more absorption bands of the sensor. The absorption band of the sensor affected by the binding of the specific analyte should overlap with the excitation band of the transducer. The high sensitivity of fluorescence detection combined with the use of proteins as highly selective sensors makes this method a powerful basis for the development of a new generation of analytical assays. Proof-of-principle results showing that cytochrome c peroxidase (CcP) for NO detection and myoglobin (Mb) for O2 detection can be successfully used by exploiting our new methodology are reported. The proposed technology can be easily expanded to the determination of different target analytes.

Synthesis and investigation of various properties of a novel series of nonlinear optical (NLO) chromophores bearing dicyanovinyl (DCV) moiety

NASA Astrophysics Data System (ADS)

Seferoğlu, Nurgul; Bayrak, Yasmina; Yalçın, Ergin; Seferoğlu, Zeynel

2017-12-01

A series of new nonlinear optic (NLO) chromophores containing a dimethine (vinyl) as π-bridge and electron acceptor dicyanomethine and different electron-donating groups and heterocyclic rings were synthesized. The structures of synthesized dyes were characterized by Fourier Transform Infrared (FTIR), proton and carbon nuclear magnetic resonance (1H/13C NMR) and mass spectrometry. Their electronic absorption spectra were evaluated in MeOH, THF and DCM. The absorption maxima exhibited little bathochromic shifts for each dye with the increasing dielectric constants of the solvents. The synthesized dyes can absorb in the range of 354-506 nm. The analysis of the electronic spectra showed that the dyes having electron-donating groups or heterocyclic rings showed significant changes relative to the model dye which has no substituent on the phenyl ring. In addition, the absorption maxima moved to the longest wavelength for dye containing N,N-dibutylamino substituent. Experimental absorption wavelengths for the compounds were found to be in good agreement with those predicted using the Time-Dependent Density Functional Theory (TD-DFT) [B3LYP/6-311 + g(d,p)]. Furthermore, the second order NLO responses of the dyes were calculated using density functional theory (DFT) calculations. The study reveals that the synthesized chromophores have large first hyperpolarizability (β) values, hence they may have potential applications in the development of NLO materials. For determination of the thermal behaviors of the compounds, thermogravimetric analysis (TGA) were done. The result showed that all the chromophores exhibited good thermal stabilities with the decomposition temperatures (Td) greater than 260 °C.

A modified commercial ultrasound scanner used for in vivo photoacoustic imaging of nude mice injected with non-targeted contrast agents

NASA Astrophysics Data System (ADS)

Jankovic, Ladislav; Shahzad, Khalid; Wang, Yao; Burcher, Michael; Scholle, Frank-Detlef; Hauff, Peter; Mofina, Sabine; Skobe, Mihaela

2008-02-01

Photoacoustic (PA) experiments were performed using a modified commercial ultrasound scanner equipped with an array transducer and a Nd:YAG pumped OPO laser. The contrast agent SIDAG (Bayer Schering Pharma AG, Germany), used to enhance the optical absorption, demonstrated an expected pharmacokinetic behavior of the dye in the tumor and in the bladder of the nude mice. A typical behavior in the tumor consisted of an initial linear increase in PA signal followed by an exponential decay. PA signal approached the pre-injection level after about one hour following the dye injection, which was consistent with the behavior for such contrast agents when used in other imaging modalities, such as fluorescence imaging. The in-vivo spectral PA data from the mouse bladder, conducted 1.5 hours after the dye injection, clearly demonstrated presence of the dye. The multi-spectral PA data was obtained at 760nm, 784nm and 850nm laser excitations. The PA intensities obtained at these three wavelengths accurately matched the dye absorption spectrum. In addition, in the kidney, a clearance organ for this contrast agent, both in-vivo and ex-vivo results demonstrated a significant increase (~ 40%) in the ratio of PA signal at 760nm (the peak of the dye absorption) relative to the signal at 850nm (<1% absorption), indicating significant amounts of the dye in this organ. Our initial results confirm the desired photoacoustic properties of the contrast agent, indicating its great potential to be used for imaging with a commercial array-based ultrasound scanner.

Application of Temperature-Dependent Fluorescent Dyes to the Measurement of Millimeter Wave Absorption in Water Applied to Biomedical Experiments

PubMed Central

Popenko, Oleksandr

2014-01-01

Temperature sensitivity of the fluorescence intensity of the organic dyes solutions was used for noncontact measurement of the electromagnetic millimeter wave absorption in water. By using two different dyes with opposite temperature effects, local temperature increase in the capillary that is placed inside a rectangular waveguide in which millimeter waves propagate was defined. The application of this noncontact temperature sensing is a simple and novel method to detect temperature change in small biological objects. PMID:25435859

Application of temperature-dependent fluorescent dyes to the measurement of millimeter wave absorption in water applied to biomedical experiments.

PubMed

Kuzkova, Nataliia; Popenko, Oleksandr; Yakunov, Andrey

2014-01-01

Temperature sensitivity of the fluorescence intensity of the organic dyes solutions was used for noncontact measurement of the electromagnetic millimeter wave absorption in water. By using two different dyes with opposite temperature effects, local temperature increase in the capillary that is placed inside a rectangular waveguide in which millimeter waves propagate was defined. The application of this noncontact temperature sensing is a simple and novel method to detect temperature change in small biological objects.

Synthesis and spectral properties of preorganized BODIPYs in solutions and Langmuir-Schaefer films

NASA Astrophysics Data System (ADS)

Marfin, Yuriy S.; Usoltsev, Sergey D.; Kazak, Alexandr V.; Smirnova, Antonina I.; Rumyantsev, Evgeniy V.; Molchanov, Evgeniy E.; Kuznetsov, Vladimir V.; Chumakov, Alexey S.; Glukhovskoy, Evgeny G.

2017-12-01

In order to investigate the influence of molecular structure peculiarities of boron-dipyrrine dyes (BODIPYs) on their properties in solutions and supramolecular organization in Langmuir-Schaefer (LS) films, four new BODIPY dyes with various aliphatic, aromatic or mixed nature meso-subtituents were synthesized and investigated. Spectral characteristics (electronic absorption and fluorescence) of the synthesized compounds in organic solvents and LS-films were studied. Floating monolayers of the BODIPYs were formed from chloroform solutions placed onto water subphase in Langmuir-Blodgett through. Thin films were prepared using the Langmuir-Schaefer technique by the transfer of floating monolayers onto standard polished glass, ITO covered glass or pure silicon substrate. The variation of the dye structure we consider as a preorganization aiming to influence the structure of LS-films. The morphology and structure of the LS-films was examined by fluorescent microscopy, scanning electron microscopy, atomic force microscopy and small angle X-ray diffraction analysis. It was found that the introduced substituents have no substantial influence on the position of the absorption and fluorescence bands in dilute solutions. In contrast, the fluorescent characteristics of the LS-films significantly depend on the substituent nature. Therefore, this strategy could be used for the direct tuning of compounds fluorescent properties in LS-films. Concerning the LS-film surface characteristics it was proved that the films are homogeneous, without disruptions and only some widely-spaced microcrystals could be observed. With respect to the LS-film structure, the change of the substituents introduced to the BODIPY molecule did not influence the average given periodicity of layers (d = 0.3-0.4 nm). This value corresponds to a single-layer arrangement of BODIPY molecules located parallel to the substrate surface. Nevertheless, the diffraction peak intensities depended on the molecular structure of BODIPYs and therefore the structurization in thin films. Moreover, the combination of the rigid phenyl moiety with long alkyl chains in one compound completely suppresses the aggregation of molecules maintaining the intense fluorescence in thin films. On the basis of used range of experimental and calculation methods the intralayer and interlayer structures were proposed. Intermolecular hydrogen bond formation and π-π staking of the BODIPY cores were found to be the structure forming forces during the films manufacturing, resulting the differences in crystallinity of the materials. While the alkyl-substituents prevent the type of interactions and suppress the association of the dyes and formation of excimers. Compounds under investigation show a manifestation of the intense solvatochromic properties which allow their application as sensors, including naked eye sensorics for solution polarity. Besides, the obtained results broaden prospective of functional materials usage based on BODIPY thin films as components of optoelectronics.

Determination of Spatial Distribution of Air Pollution by Dye Laser Measurement of Differential Absorption of Elastic Backscatter

NASA Technical Reports Server (NTRS)

Ahmed, S. A.; Gergely, J. S.

1973-01-01

This paper presents the results of an analytical study of a lidar system which uses tunable organic dye lasers to accurately determine spatial distribution of molecular air pollutants. Also described will be experimental work to date on simultaneous multiwavelength output dye laser sources for this system. Basically the scheme determines the concentration of air pollutants by measuring the differential absorption of an (at least) two wavelength lidar signal elastically backscattered by the atmosphere. Only relative measurements of the backscattered intensity at each of the two wavelengths, one on and one off the resonance absorption of the pollutant in question, are required. The various parameters of the scheme are examined and the component elements required for a system of this type discussed, with emphasis on the dye laser source. Potential advantages of simultaneous multiwavelength outputs are described. The use of correlation spectroscopy in this context is examined. Comparisons are also made for the use of infrared probing wavelengths and sources instead of dye lasers. Estimates of the sensitivity and accuracy of a practical dye laser system of this type, made for specific pollutants, snow it to have inherent advantages over other schemes for determining pollutant spatial distribution.

Coordination Complexes of Titanium(IV) and Indium(III) Phthalocyanines with Carbonyl-Containing Dyes: The Formation of Singly Bonded Anionic Squarylium Dimers.

PubMed

Konarev, Dmitri V; Kuzmin, Alexey V; Khasanov, Salavat S; Fatalov, Alexey M; Yudanova, Evgenia I; Lyubovskaya, Rimma N

2018-04-14

Reduction methods for the preparation of coordination complexes of titanium(IV) and indium(III) phthalocyanines (Pc) with organic dyes such as indigo, thioindigo, and squarylium dye III (SQ) have been developed, which allow one to obtain crystalline {cryptand(K + )}{(cis-indigo-O,O) 2- Ti IV (Pc 2- )}(Cl - )⋅C 6 H 4 Cl 2 (1), {cryptand(K + )}{(cis-thioindigo-O,O) 2- In III (Pc 2- )} - ⋅C 6 H 4 Cl 2 (2), and {cryptand(K + )}{[(SQ) 2 -O,O] 2- In III (Pc 2- )} - ⋅3.5 C 6 H 4 Cl 2 (3) complexes. The formation of these complexes is accompanied by the reduction of the starting dyes to the anionic state. Transition of trans-indigo or trans-thioindigo to the cis conformation in 1 and 2 provides coordination of both carbonyl oxygen atoms of the dye to Ti IV Pc or In III Pc. SQ is reduced to the radical anion state and forms unusual diamagnetic singly bonded (SQ - ) 2 dimers in 3. These dimers have two closely positioned carbonyl oxygen atoms coordinated to In III Pc. Dianionic Pc 2- macrocycles have been found in 1-3. The complexes contain two chromophore molecules at one metal center. However, their optical spectra are defined mainly by absorption bands of the metal phthalocyanines. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of twisted D–D–π–A configuration on electron transfer and photo-physics characteristics

NASA Astrophysics Data System (ADS)

Liu, Yunpeng; Li, Yuanzuo; Song, Peng; Ma, Fengcai; Yang, Yanhui

2018-05-01

Two D-D-π-A organic dyes (M45, M46) with dithieno[3,2-b:2‧,3‧-d]pyrrole (DTP) units as election donors in two perpendicular directions, were investigated using density functional theory (DFT) and time-dependent DFT. The ground-state geometries, the absorption, the electronic structures, the charge density difference and molecular electrostatic potential were obtained. To simulate a more realistic performance, all calculations were based on gas condition and dichloromethane solvent. Photoelectric parameters were evaluated by the following factors: the light harvesting efficiency, electron injection driving force, the excited lifetime and vertical dipole moment. Meanwhile, the polarisability and hyperpolarisability were investigated to further explain the relationship between non-linear optical properties and efficiency. The direction of the DTP obviously affects the twisted degree of molecule, forming a better coplanarity on the donor 2 of M45, which results in stronger charge transfer interactions. Furthermore, M45 possesses significant advantages in geometric structure, absorption band and intramolecular charge transfer mechanism. These critical parameters supported the higher performance of M45 in comparison with M46. Moreover, four dyes were designed by the substitution of donor 2, which further verify the influence of the twisted donor 2 on electron transfer and photoelectric properties of D-D-π-A configuration.

Photoinduced electron transfer (PET) versus excimer formation in supramolecular p/n-heterojunctions of perylene bisimide dyes and implications for organic photovoltaics.

PubMed

Nowak-Król, Agnieszka; Fimmel, Benjamin; Son, Minjung; Kim, Dongho; Würthner, Frank

2015-01-01

Foldamer systems comprised of two perylene bisimide (PBI) dyes attached to the conjugated backbones of 1,2-bis(phenylethynyl)benzene and phenylethynyl-bis(phenylene)indane, respectively, were synthesized and investigated with regard to their solvent-dependent properties. UV/Vis absorption and steady-state fluorescence spectra show that both foldamers exist predominantly in a folded H-aggregated state consisting of π-π-stacked PBIs in THF and in more random conformations with weaker excitonic coupling between the PBIs in chloroform. Time-resolved fluorescence spectroscopy and transient absorption spectroscopy reveal entirely different relaxation pathways for the photoexcited molecules in the given solvents, i.e. photoinduced electron transfer leading to charge separated states for the open conformations (in chloroform) and relaxation into excimer states with red-shifted emission for the stacked conformations (in THF). Supported by redox data from cyclic voltammetry and Rehm-Weller analysis we could relate the processes occurring in these solution-phase model systems to the elementary processes in organic solar cells. Accordingly, only if relaxation pathways such as excimer formation are strictly avoided in molecular semiconductor materials, excitons may diffuse over larger distances to the heterojunction interface and produce photocurrent via the formation of electron/hole pairs by photoinduced electron transfer.

A new molecular model for Congo Red-β amyloid interaction: implications for diagnosis and inhibition of brain plaque formation in Alzheimer's disease

NASA Astrophysics Data System (ADS)

Zhang, Kristine A.; Li, Yat

2015-08-01

Alzheimer's disease (AD), an age-related neurodegenerative disorder, is the seventh leading cause of death in the United States. One strong pathological indicator of AD is senile plaques, which are aggregates of fibrils formed from amyloid β (Aβ) peptides. Thus, detection and inhibition of Aβ aggregation are critical for the prevention and treatment of AD. Congo red (CR) is one of the most widely used dye molecules for probing as well as inhabiting Aβ aggregation. However, the nature of interaction between CR and Aβ is not well understood. In this research, we systematically studied the interaction between CR and Aβ using a combination of optical techniques, including electronic absorption, fluorescence, Raman scattering, and circular dichroism, to provide detailed information with molecular specificity and high sensitivity. Compared to CR alone, interaction of the dye with Aβ results in a new absorption peak near 540 nm and significantly enhanced photoluminescence as well as Raman signal. Our results led us to propose a new model suggesting that CR exists primarily in a micellar form, resembling H-aggregates, in water and dissociates into monomers upon interaction with Aβ. This model has significant implications for the development of new strategies to detect and inhibit brain plaques for treatment of neurological diseases like AD.

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1998-01-13

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution. 7 figs.

Monitoring Ultrafast Chemical Dynamics by Time-Domain X-ray Photo- and Auger-Electron Spectroscopy.

PubMed

Gessner, Oliver; Gühr, Markus

2016-01-19

The directed flow of charge and energy is at the heart of all chemical processes. Extraordinary efforts are underway to monitor and understand the concerted motion of electrons and nuclei with ever increasing spatial and temporal sensitivity. The element specificity, chemical sensitivity, and temporal resolution of ultrafast X-ray spectroscopy techniques hold great promise to provide new insight into the fundamental interactions underlying chemical dynamics in systems ranging from isolated molecules to application-like devices. Here, we focus on the potential of ultrafast X-ray spectroscopy techniques based on the detection of photo- and Auger electrons to provide new fundamental insight into photochemical processes of systems with various degrees of complexity. Isolated nucleobases provide an excellent testing ground for our most fundamental understanding of intramolecular coupling between electrons and nuclei beyond the traditionally applied Born-Oppenheimer approximation. Ultrafast electronic relaxation dynamics enabled by the breakdown of this approximation is the major component of the nucleobase photoprotection mechanisms. Transient X-ray induced Auger electron spectroscopy on photoexcited thymine molecules provides atomic-site specific details of the extremely efficient coupling that converts potentially bond changing ultraviolet photon energy into benign heat. In particular, the time-dependent spectral shift of a specific Auger band is sensitive to the length of a single bond within the molecule. The X-ray induced Auger transients show evidence for an electronic transition out of the initially excited state within only ∼200 fs in contrast to theoretically predicted picosecond population trapping behind a reaction barrier. Photoinduced charge transfer dynamics between transition metal complexes and semiconductor nanostructures are of central importance for many emerging energy and climate relevant technologies. Numerous demonstrations of photovoltaic and photocatalytic activity have been performed based on the combination of strong light absorption in dye molecules with charge separation and transport in adjacent semiconductor nanostructures. However, a fundamental understanding of the enabling and limiting dynamics on critical atomic length- and time scales is often still lacking. Femtosecond time-resolved X-ray photoelectron spectroscopy is employed to gain a better understanding of a short-lived intermediate that may be linked to the unexpectedly limited performance of ZnO based dye-sensitized solar cells by delaying the generation of free charge carriers. The transient spectra strongly suggest that photoexcited dye molecules attached to ZnO nanocrystals inject their charges into the substrate within less than 1 ps but the electrons are then temporarily trapped at the surface of the semiconductor in direct vicinity of the injecting molecules. The experiments are extended to monitor the electronic response of the semiconductor substrate to the collective injection from a monolayer of dye molecules and the subsequent electron-ion recombination dynamics. The results indicate some qualitative similarities but quantitative differences between the recombination dynamics at molecule-semiconductor interfaces and previously studied bulk-surface electron-hole recombination dynamics in photoexcited semiconductors.

Giant light-harvesting nanoantenna for single-molecule detection in ambient light

PubMed Central

Trofymchuk, Kateryna; Reisch, Andreas; Didier, Pascal; Fras, François; Gilliot, Pierre; Mely, Yves; Klymchenko, Andrey S.

2017-01-01

Here, we explore the enhancement of single molecule emission by polymeric nano-antenna that can harvest energy from thousands of donor dyes to a single acceptor. In this nano-antenna, the cationic dyes are brought together in very close proximity using bulky counterions, thus enabling ultrafast diffusion of excitation energy (≤30 fs) with minimal losses. Our 60-nm nanoparticles containing >10,000 rhodamine-based donor dyes can efficiently transfer energy to 1-2 acceptors resulting in an antenna effect of ~1,000. Therefore, single Cy5-based acceptors become 25-fold brighter than quantum dots QD655. This unprecedented amplification of the acceptor dye emission enables observation of single molecules at illumination powers (1-10 mW cm-2) that are >10,000-fold lower than typically required in single-molecule measurements. Finally, using a basic setup, which includes a 20X air objective and a sCMOS camera, we could detect single Cy5 molecules by simply shining divergent light on the sample at powers equivalent to sunlight. PMID:28983324

Thermal behavior of H-aggregate in a mixed Langmuir-Blodgett film of merocyanine dye, arachidic acid, and n-octadecane ternary system investigated by UV-visible and IR absorption spectroscopy.

PubMed

Hirano, Yoshiaki; Tateno, Shinsuke; Yamashita, Yoshihide; Ozaki, Yukihiro

2008-11-13

We have investigated the thermal behavior of H-aggregate in a mixed Langmuir-Blodgett (LB) film of the merocyanine dye (MS18)-arachidic acid (C20)- n-octadecane (AL18) ternary system by means of UV-visible and IR absorption spectroscopy in the range from 25 to 250 degrees C with a continuous scan. The results of both UV-visible and IR spectra indicate that the temperature-dependent variation in MS 18 aggregation state is linked not only with the degree of intramolecular charge transfer and the behavior of packing, orientation, conformation, and thermal mobility of the MS18 hydrocarbon chain but also with the presence and absence of AL18. The H-aggregate dissociates from 25 up to 50 degrees C, which is caused by the AL18 evaporation from the mixed LB film and the increment of thermal mobility of the MS18 hydrocarbon chain. From 110 to 160 degrees C, blue-shifted bands, attributed to the oligomeric MS18 aggregation, appear near 515 nm in the MS18-C 20-AL18 ternary system as well. The temperature at which the 515 nm band occurs is identical for both present ternary system and previously investigated MS18-deuterated arachidic acid (C20- d) binary system, and it is in good agreement with the melting point (110 degrees C) of cadmium arachidate (CdC20). Therefore, it is indicated that the driving force which induces the 515 nm band comes from the melting phenomenon of CdC20 molecules which are phase-separated from MS 18 molecules in as-deposited LB films.

Quantum Dot-Based Hybrid Nanostructures and Energy Transfer on the Nanoscale for Single- and Multi-Photon Imaging and Cancer Diagnostics

NASA Astrophysics Data System (ADS)

Nabiev, Igor

2017-01-01

An ideal single-photon (1P) or multiphoton fluorescent nanoprobe should combine a nanocrystal with the largest possible 1P or two-photon (2P) absorption cross section and the smallest possible highly specific recognition molecules conjugated with the nanoparticle in an oriented manner. However, the conditions used for conjugation of typical recognition molecules (conventional antibodies, Abs) with nanoparticles often provoke their unfolding and/or yield nanoprobes with irregular orientation of Abs on the nanoparticle surface. Conjugation of smaller Ab fragments, such as single-domain antibodies (sdAbs), with quantum dots (QDs) in an oriented manner can be considered as an attractive approach to engineering of ultrasmall diagnostic nanoprobes. QDs conjugated to 13-kDa sdAbs derived from camelid IgG or streptavidin have been used as efficient 1P or 2P excitation probes for imaging of cancer markers. The 2P absorption cross sections (TPACSs) for some conjugates are higher than 49,000 GM (Goeppert-Mayer units), which is close to the theoretical value calculated for CdSe QDs and considerably exceeds that of organic dyes. A further step in advanced QD-based cancer diagnostics has been made through implementation of efficient FRET-based imaging with 2P excitation, which has been demonstrated for double immunostaining complexes formed on the surface of cancer cells from sdAb-QD conjugates (donor) and a combination of monoclonal Abs and secondary antibodies labeled with the AlexaFluor dye (acceptor). The proposed approach permits obtaining an exceptional contrast of 2P imaging of cancer biomarkers without any contribution of cell and tissue autofluorescence in the recorded images.

Solar generation and storage of O2 (a 1 delta g)

NASA Technical Reports Server (NTRS)

Twarowski, Allen J.; Dao, Phan; Good, Lisa A.

1988-01-01

An investigation was performed of the technical steps required to design a solar powered oxygen-iodine laser. Singlet delta oxygen is formed upon transfer of energy from selected photoexcited dye molecules to ground state molecular oxygen and then is concentrated and stored as an endoperoxide by reaction with an aromatic hydrocarbon. The endoperoxide, when heated, releases singlet oxygen in high yield thus providing a regenerable source of laser fuel. Energy transfer from dye molecules to molecular oxygen was investigated. When dye molecules were adsorbed to polymer substrates it was observed that the dye became embedded in the polymer matrix. Porphin dyes were incorporated into films of 1,4-dimethyl-2-poly(vinylnaphthalene), 2PVN. An endoperoxide was formed when porphin-doped 2PVN was exposed to visible radiation. This demonstrates the possibility of generating singlet oxygen using solar energy and concentrating and storing it in one simple step. Transport of energy by exciton migration in polycrystalline dye films was also investigated.

Polylactic acid promotes healing of photodegraded disperse orange 11 molecules

NASA Astrophysics Data System (ADS)

Stubbs, Najee; Bridgewater, Mauricio; Stubbs, Micheala; Kabir, Amin; Crescimanno, Michael; Kuzyk, Mark G.; Dawson, Nathan J.

2018-02-01

We report on the recovery of a photodegraded organic molecule mediated by a biopolymer. Amplified spontaneous emission (ASE) from disperse orange 11 (DO11) dye-doped polylactic acid (PLA) was used to monitor photodegradation while the material was being damaged by a strong pump laser. The ASE signal fully recovers over two hours time when the pump beam is blocked. The fluorescence spectra was also observed to recover after partial photobleaching the dye-doped polymer. PLA is the first biopolymer known to mediate the recovery of a photodegraded organic dye molecule.

High Affinity Macrocycle Threading by a Near-Infrared Croconaine Dye with Flanking Polymer Chains

PubMed Central

Liu, Wenqi; Peck, Evan M.; Smith, Bradley D.

2016-01-01

Croconaine dyes have narrow and intense absorption bands at ~800 nm, very weak fluorescence, and high photostabilities, which combine to make them very attractive chromophores for absorption-based imaging or laser heating technologies. The physical supramolecular properties of croconaine dyes have rarely been investigated, especially in water. This study focuses on a molecular threading process that encapsulates a croconaine dye inside a tetralactam macrocycle in organic or aqueous solvent. Macrocycle association and rate constant data are reported for a series of croconaine structures with different substituents attached to the ends of the dye. The association constants were highest in water (Ka ~109 M−1), and the threading rate constants (kon) increased in the solvent order H2O > MeOH > CHCl3. Systematic variation of croconaine substituents located just outside the croconaine/macrocycle complexation interface hardly changed Ka but had a strong influence on kon. A croconaine dye with N-propyl groups at each end of the structure exhibited a desirable mixture of macrocycle threading properties; that is, there was rapid and quantitative croconaine/macrocycle complexation at relatively high concentrations in water, and no dissociation of the pre-assembled complex when it was diluted into a solution of fetal bovine serum, even after laser induced photothermal heating of the solution. The combination of favorable near-infrared absorption properties and tunable mechanical stability makes threaded croconaine/macrocycle complexes very attractive as molecular probes or as supramolecular composites for various applications in absorption-based imaging or photothermal therapy. PMID:26807599

Synthesis, structural characterization and tautomeric properties of some novel bis-azo dyes derived from 5-arylidene-2,4-thiazolidinone

NASA Astrophysics Data System (ADS)

Mohammadi, Asadollah; Safarnejad, Mastaneh

Nine new bis-azo dyes derived from 5-arylidene-2,4-thiazolidinone have been synthesized in two steps using Knoevenagel condensation and diazotization-coupling reaction. The structures of the compounds were confirmed by UV-vis, IR, 1H NMR and 13C NMR spectroscopic techniques. The spectral characterizations demonstrate that there is an equilibrium between the azo (T1) and hydrazine (T2 and T3) tautomers for all prepared dyes in solutions. In addition, the solvatochromic behavior of the prepared dyes was evaluated using polarity/polarizability parameter (π*) in various solvents. The UV-vis absorption spectra of dyes show a bathochromic shift with increasing polarity and base strength of the solvents. Finally, the effects of acid and base on the UV-vis absorption spectra of the dyes with different substituent in diazo component are reported.

Versatile three-dimensional virus-based template for dye-sensitized solar cells with improved electron transport and light harvesting.

PubMed

Chen, Po-Yen; Dang, Xiangnan; Klug, Matthew T; Qi, Jifa; Dorval Courchesne, Noémie-Manuelle; Burpo, Fred J; Fang, Nicholas; Hammond, Paula T; Belcher, Angela M

2013-08-27

By genetically encoding affinity for inorganic materials into the capsid proteins of the M13 bacteriophage, the virus can act as a template for the synthesis of nanomaterial composites for use in various device applications. Herein, the M13 bacteriophage is employed to build a multifunctional and three-dimensional scaffold capable of improving both electron collection and light harvesting in dye-sensitized solar cells (DSSCs). This has been accomplished by binding gold nanoparticles (AuNPs) to the virus proteins and encapsulating the AuNP-virus complexes in TiO2 to produce a plasmon-enhanced and nanowire (NW)-based photoanode. The NW morphology exhibits an improved electron diffusion length compared to traditional nanoparticle-based DSSCs, and the AuNPs increase the light absorption of the dye-molecules through the phenomenon of localized surface plasmon resonance. Consequently, we report a virus-templated and plasmon-enhanced DSSC with an efficiency of 8.46%, which is achieved through optimizing both the NW morphology and the concentration of AuNPs loaded into the solar cells. In addition, we propose a theoretical model that predicts the experimentally observed trends of plasmon enhancement.

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.

Theoretical studies on effective metal-to-ligand charge transfer characteristics of novel ruthenium dyes for dye sensitized solar cells.

PubMed

Wang, Huei-Tang; Taufany, Fadlilatul; Nachimuthu, Santhanamoorthi; Jiang, Jyh-Chiang

2014-05-01

The development of ruthenium dye-sensitizers with highly effective metal-to-ligand charge transfer (MLCT) characteristics and narrowed transition energy gaps are essential for the new generation of dye-sensitized solar cells. Here, we designed a novel anchoring ligand by inserting the cyanovinyl-branches inside the anchoring ligands of selected highly efficient dye-sensitizers and studied their intrinsic optical properties using theoretical methods. Our calculated results show that the designed ruthenium dyes provide good performances as sensitizers compared to the selected efficient dyes, because of their red-shift in the UV-visible absorption spectra with an increase in the absorption intensity, smaller energy gaps and thereby enhancing MLCT transitions. We found that, the designed anchoring ligand acts as an efficient "electron-acceptor" which boosts electron-transfer from a -NCS ligand to this ligand via a Ru-bridge, thus providing a way to lower the transition energy gap and enhance the MLCT transitions.

A deeper insight into an intriguing acetonitrile-water binary mixture: synergistic effect, dynamic Stokes shift, fluorescence correlation spectroscopy, and NMR studies.

PubMed

Koley, Somnath; Ghosh, Subhadip

2016-11-30

An insight study reveals the strong synergistic solvation behaviours from reporter dye molecules within the acetonitrile (ACN)-water (WT) binary mixture. Synergism of a binary mixture refers to some unique changes of the physical and thermodynamic properties of the solvent mixture, originating from the interactions among its cosolvents, which are absent within the pure cosolvents. Synergistic solvation of a binary mixture is likely to be fundamental for greater stabilization of an excited state solute dipole; at least to some extent greater as compared to one stabilized by any of its cosolvents alone. A dynamic Stokes shift due to the solvation of an excited dipole in the ACN-WT binary mixture is found to be highly relevant to the ground state physical properties of the solute molecule (polarity, hydrophilicity, acidity, etc.). Largely different solvation times in the ACN-WT mixture are observed from different dye molecules with widely varying polarities. However, earlier study shows that dye molecules, irrespective of their varying polarities, exhibit very similar solvation times within a pure solvent (J. Phys. Chem. B, 2014, 118, 7577-7785). On further study with fluorescence correlation spectroscopy (FCS) we observed that, unlike the translational diffusion coefficient (D t ) of a dye molecule within a pure solvent, which remains the same irrespective of the location of the dye molecule inside the solvent, a broad distribution among the D t values of a dye molecule is obtained from different locations within the ACN-WT binary mixture. Lastly our 1 H NMR study in the ACN-WT binary mixture shows the existence of strong hydrogen bond interactions among the cosolvents in the ACN-WT mixture.

Amino Acid-Assisted Incorporation of Dye Molecules within Calcite Crystals.

PubMed

Marzec, Bartosz; Green, David C; Holden, Mark A; Coté, Alexander S; Ihli, Johannes; Khalid, Saba; Kulak, Alexander; Walker, Daniel; Tang, Chiu; Duffy, Dorothy M; Kim, Yi-Yeoun; Meldrum, Fiona C

2018-05-23

Biomineralisation processes invariably occur in the presence of multiple organic additives, which act in combination to give exceptional control over structures and properties. However, few synthetic studies have investigated the cooperative effects of soluble additives. This work addresses this challenge and focuses on the combined effects of amino acids and coloured dye molecules. The experiments demonstrate that strongly coloured calcite crystals only form in the presence of Brilliant Blue R (BBR) and four of the seventeen soluble amino acids, as compared with almost colourless crystals using the dye alone. The active amino acids are identified as those which themselves effectively occlude in calcite, suggesting a mechanism where they can act as chaperones for individual molecules or even aggregates of dyes molecules. These results provide new insight into crystal-additive interactions and suggest a novel strategy for generating materials with target properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DFT/TD-semiempirical study on the structural and electronic properties and absorption spectra of supramolecular fullerene-porphyrine-metalloporphyrine triads based dye-sensitized solar cells.

PubMed

Rezvani, M; Darvish Ganji, M; Jameh-Bozorghi, S; Niazi, A

2018-04-05

In the present work density functional theory (DFT) and time-dependent semiempirical ZNIDO/S (TD-ZNIDO/S) methods have been used to investigate the ground state geometries, electronic structures and excited state properties of triad systems. The influences of the type of metal in the porphyrin ring, change in bridge position and porphyrine-ZnP duplicate on the energies of frontier molecular orbital and UV-Vis spectra has been studied. Geometry optimization, the energy levels and electron density of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), chemical hardness (η), electrophilicity index (ω), electron accepting power (ω + ) were calculated using ZINDO/S method to predict which molecule is the most efficient with a great capability to be used as a triad molecule in solar industry. Moreover the light harvesting efficiency (LHE) was calculated by means of the oscillator strengths which are obtained by TD-ZINDO/S calculation. Theoretical studies of the electronic spectra by ZINDO/S method were helpful in interpreting the observed electronic transitions. This aspect was systematically explored in a series of C 60 -Porphyrine-Metalloporphyrine (C 60 -P-Mp) triad system with M being Fe, Co, Ni, Ti, and Zn. Generally, transition metal coordination compounds are used as effective sensitizers, due to their intense charge-transfer absorption over the whole visible range and highly efficient metal-to-ligand charge transfer. We aim to optimize the performance of the title solar cells by altering the frontier orbital energy gaps. The results reveal that cell efficiency can be enhanced by metal functionalization of the free base porphyrin. Ti-porphyrin was found to be the most efficient dye sensitizer for dye sensitized solar cells (DSSCs) based on C 60 -P-Mptriad system due to C 60 -Por-TiP complex has lower chemical hardness, gap energy and chemical potential as well as higher electron accepting power among other complexes. In addition, the performance of solar cells favors better with doubly and increasing the π conjugated of the bridge. Copyright © 2018 Elsevier B.V. All rights reserved.

DFT/TD-semiempirical study on the structural and electronic properties and absorption spectra of supramolecular fullerene-porphyrine-metalloporphyrine triads based dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Rezvani, M.; Darvish Ganji, M.; Jameh-Bozorghi, S.; Niazi, A.

2018-04-01

In the present work density functional theory (DFT) and time-dependent semiempirical ZNIDO/S (TD-ZNIDO/S) methods have been used to investigate the ground state geometries, electronic structures and excited state properties of triad systems. The influences of the type of metal in the porphyrin ring, change in bridge position and porphyrine-ZnP duplicate on the energies of frontier molecular orbital and UV-Vis spectra has been studied. Geometry optimization, the energy levels and electron density of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), chemical hardness (η), electrophilicity index (ω), electron accepting power (ω+) were calculated using ZINDO/S method to predict which molecule is the most efficient with a great capability to be used as a triad molecule in solar industry. Moreover the light harvesting efficiency (LHE) was calculated by means of the oscillator strengths which are obtained by TD-ZINDO/S calculation. Theoretical studies of the electronic spectra by ZINDO/S method were helpful in interpreting the observed electronic transitions. This aspect was systematically explored in a series of C60-Porphyrine-Metalloporphyrine (C60-P-Mp) triad system with M being Fe, Co, Ni, Ti, and Zn. Generally, transition metal coordination compounds are used as effective sensitizers, due to their intense charge-transfer absorption over the whole visible range and highly efficient metal-to-ligand charge transfer. We aim to optimize the performance of the title solar cells by altering the frontier orbital energy gaps. The results reveal that cell efficiency can be enhanced by metal functionalization of the free base porphyrin. Ti-porphyrin was found to be the most efficient dye sensitizer for dye sensitized solar cells (DSSCs) based on C60-P-Mptriad system due to C60-Por-TiP complex has lower chemical hardness, gap energy and chemical potential as well as higher electron accepting power among other complexes. In addition, the performance of solar cells favors better with doubly and increasing the π conjugated of the bridge.

Correlating Nanoscopic Energy Transfer and Far-Field Emission to Unravel Lasing Dynamics in Plasmonic Nanocavity Arrays

DOE PAGES

Deeb, Claire; Guo, Zhi; Yang, Ankun; ...

2018-01-25

Excited-state interactions between nanoscale cavities and photoactive molecules are critical in plasmonic nanolasing, although the underlying details are less-resolved. This paper reports direct visualization of the energy-transfer dynamics between two-dimensional arrays of plasmonic gold bowtie nanocavities and dye molecules. Transient absorption microscopy measurements of single bowties within the array surrounded by gain molecules showed fast excited-state quenching (2.6 ± 1 ps) characteristic of individual nanocavities. Upon optical pumping at powers above threshold, lasing action emerged depending on the spacing of the array. By correlating ultrafast microscopy and far-field light emission characteristics, we found that bowtie nanoparticles acted as isolated cavitiesmore » when the diffractive modes of the array did not couple to the plasmonic gap mode. These results demonstrate how ultrafast microscopy can provide insight into energy relaxation pathways and, specifically, how nanocavities in arrays can show single-unit nanolaser properties.« less

Correlating Nanoscopic Energy Transfer and Far-Field Emission to Unravel Lasing Dynamics in Plasmonic Nanocavity Arrays

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

Deeb, Claire; Guo, Zhi; Yang, Ankun

Excited-state interactions between nanoscale cavities and photoactive molecules are critical in plasmonic nanolasing, although the underlying details are less-resolved. This paper reports direct visualization of the energy-transfer dynamics between two-dimensional arrays of plasmonic gold bowtie nanocavities and dye molecules. Transient absorption microscopy measurements of single bowties within the array surrounded by gain molecules showed fast excited-state quenching (2.6 ± 1 ps) characteristic of individual nanocavities. Upon optical pumping at powers above threshold, lasing action emerged depending on the spacing of the array. By correlating ultrafast microscopy and far-field light emission characteristics, we found that bowtie nanoparticles acted as isolated cavitiesmore » when the diffractive modes of the array did not couple to the plasmonic gap mode. These results demonstrate how ultrafast microscopy can provide insight into energy relaxation pathways and, specifically, how nanocavities in arrays can show single-unit nanolaser properties.« less

Stimulated emission from aluminium anode oxide films doped with rhodamine 6G

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

Ibrayev, N Kh; Zeinidenov, A K; Aimukhanov, A K

The spectral and luminescent properties of the rhodamine 6G dye in a porous matrix of aluminium anode oxide are studied. The films with a highly-ordered porous structure are produced using the method of two-stage anodic oxidation. By means of raster electron microscopy it is found that the diameter of the pores amounts to nearly 50 nm and the separation between the adjacent channels is almost 105 nm. The thickness of the films is equal to 55 μm, and the specific surface area measured using the method of nitrogen capillary condensation is 15.3 m{sup 2} g{sup -1}. Fluorescence and absorption spectramore » of rhodamine 6G molecules injected into the pores of the aluminium anode oxide are measured. It is found that under the excitation of samples with the surface dye concentration 0.3 × 10{sup 14} molecules m{sup -2} by the second harmonic of the Nd : YAG laser in the longitudinal scheme with the pumping intensity 0.4 MW cm{sup -2}, a narrow band of stimulated emission with the intensity maximum at the wavelength 572 nm appears against the background of the laser-induced fluorescence spectrum. A further increase in the pumping radiation intensity leads to the narrowing of the stimulated emission band and an increase in its intensity. The obtained results demonstrate the potential possibility of using the porous films of aluminium anode oxide, doped with laser dyes, in developing active elements for quantum electronics. (laser applications and other topics in quantum electronics)« less

Dye-binding assays for evaluation of the effects of small molecule inhibitors on amyloid (aβ) self-assembly.

PubMed

Jameson, Laramie P; Smith, Nicholas W; Dzyuba, Sergei V

2012-11-21

Dye-binding assays, such as those utilizing Congo red and thioflavin T, are among the most widely used tools to probe the aggregation of amyloidogenic biomolecules and for the evaluation of small molecule inhibitors of amyloid aggregation and fibrillization. A number of recent reports have indicated that these dye-binding assays could be prone to false positive effects when assessing inhibitors' potential toward Aβ peptides, species involved in Alzheimer's disease. Specifically, this review focuses on the application of thioflavin T for determining the efficiency of small molecule inhibitors of Aβ aggregation and addresses potential reasons that might be associated with the false positive effects in an effort to increase reliability of dye-binding assays.

Dye-Binding Assays for Evaluation of the Effects of Small Molecule Inhibitors on Amyloid (Aβ) Self-Assembly

PubMed Central

2012-01-01

Dye-binding assays, such as those utilizing Congo red and thioflavin T, are among the most widely used tools to probe the aggregation of amyloidogenic biomolecules and for the evaluation of small molecule inhibitors of amyloid aggregation and fibrillization. A number of recent reports have indicated that these dye-binding assays could be prone to false positive effects when assessing inhibitors’ potential toward Aβ peptides, species involved in Alzheimer’s disease. Specifically, this review focuses on the application of thioflavin T for determining the efficiency of small molecule inhibitors of Aβ aggregation and addresses potential reasons that might be associated with the false positive effects in an effort to increase reliability of dye-binding assays. PMID:23173064

Teaching Old Dyes New Tricks: Biological Probes Built from Fluoresceins and Rhodamines.

PubMed

Lavis, Luke D

2017-06-20

Small-molecule fluorophores, such as fluorescein and rhodamine derivatives, are critical tools in modern biochemical and biological research. The field of chemical dyes is old; colored molecules were first discovered in the 1800s, and the fluorescein and rhodamine scaffolds have been known for over a century. Nevertheless, there has been a renaissance in using these dyes to create tools for biochemistry and biology. The application of modern chemistry, biochemistry, molecular genetics, and optical physics to these old structures enables and drives the development of novel, sophisticated fluorescent dyes. This critical review focuses on an important example of chemical biology-the melding of old and new chemical knowledge-leading to useful molecules for advanced biochemical and biological experiments.

Laser-induced emission spectroscopy of matrix-isolated carbon molecules: Experimental setup and new results on C3

NASA Astrophysics Data System (ADS)

Čermák, Ivo; Förderer, Markus; Čermáková, Iva; Kalhofer, Stefan; Stopka-Ebeler, Helmut; Monninger, Gerold; Krätschmer, Wolfgang

1998-06-01

We have studied small carbon molecules using a matrix-isolation technique. Our experimental setup is described in detail. The carbon clusters were produced by evaporating graphite and trapping the carbon-vapor molecules in solid argon, where molecular growth could be induced by controlled matrix annealing. To identify the produced molecules, absorption spectroscopy in the ultraviolet (UV)-visible and infrared (IR) spectral ranges was applied. Additional characterization of the excited and ground states of the molecules was obtained from emission and excitation spectra. The molecules were excited by a pulsed dye laser system and the emission spectra were recorded with a high-sensitivity photodiode-array spectrometer. We present our measurements on linear C3. The à 1Πu excited state of linear C3 was populated by the electronic transition à 1Πu←X˜ 1Σg+, and the corresponding excitation spectra of the C3 fluorescence (à 1Πu→X˜ 1Σg+) and phosphorescence (ã 3Πu→X˜ 1Σg+) were studied. Comparison of excitation and absorption spectra yielded information on site effects due to the matrix environment. Emission bands in the fluorescence and phosphorescence spectra up to vibrational energies of 8500 cm-1 could be observed. The radiation lifetime of the à 1Πu excited state of C3 in solid argon was found to be shorter than 10 ns. The phosphorescence transition ã 3Πu→X˜ 1Σg+ decays in about 10 ms and its rise indicates fast vibrational relaxation within the triplet system. Our data support a linear ground state geometry for C3 also in solid argon.

Why Congo red binding is specific for amyloid proteins - model studies and a computer analysis approach.

PubMed

Roterman, I; KrUl, M; Nowak, M; Konieczny, L; Rybarska, J; Stopa, B; Piekarska, B; Zemanek, G

2001-01-01

The complexing of Congo red in two different ligand forms - unimolecular and supramolecular (seven molecules in a micelle) - with eight deca-peptides organized in a b-sheet was tested by computational analysis to identify its dye-binding preferences. Polyphenylananine and polylysine peptides were selected to represent the specific side chain interactions expected to ensure particularly the stabilization of the dye-protein complex. Polyalanine was used to verify the participation of non-specific backbone-derived interactions. The initial complexes for calculation were constructed by intercalating the dye between the peptides in the middle of the beta-sheet. The long axis of the dye molecule (in the case of unimolecular systems) or the long axis of the ribbon-like micelle (in the case of the supramolecular dye form) was oriented parallel to the peptide backbone. This positioning maximally reduced the exposure of the hydrophobic diphenyl (central dye fragment) to water. In general the complexes of supramolecular Congo red ligands appeared more stable than those formed by individual dye molecules. Specific interactions (electrostatic and/or ring stacking) dominated as binding forces in the case of the single molecule, while non-specific surface adsorption seemed decisive in complexing with the supramolecular ligand. Both the unimolecular and supramolecular versions of the dye ligand were found to be likely to form complexes of sufficient stability with peptides. The low stability of the protein and the gap accessible to penetration in the peptide sheet seem sufficient for supramolecular ligand binding, but the presence of positively charged or hydrophobic amino acids may strengthen binding significantly. The need for specific interaction makes single-molecule Congo red binding rather unusual as a general amyloid protein ligand. The structural feature of Congo red, which enables specific and common interaction with amyloid proteins, probably derives from the ribbon-like self-assembled form of the dye.

Broad band nonlinear optical absorption measurements of the laser dye IR26 using white light continuum Z-scan

NASA Astrophysics Data System (ADS)

Dey, Soumyodeep; Bongu, Sudhakara Reddy; Bisht, Prem Ballabh

2017-03-01

We study the nonlinear optical response of a standard dye IR26 using the Z-scan technique, but with the white light continuum. The continuum source of wavelength from 450 nm to 1650 nm has been generated from the photonic crystal fiber on pumping with 772 nm of Ti:Sapphire oscillator. The use of broadband incident pulse enables us to probe saturable absorption (SA) and reverse saturable absorption (RSA) over the large spectral range with a single Z-scan measurement. The system shows SA in the resonant region while it turns to RSA in the non-resonant regions. The low saturation intensity of the dye can be explained based on the simultaneous excitation from ground states to various higher energy levels with the help of composite energy level diagram. The cumulative effects of excited state absorption and thermal induced nonlinear optical effects are responsible for the observed RSA.

Tuning the photophysical properties of BODIPY dyes through extended aromatic pyrroles

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

Swavey, Shawn; Quinn, John; Coladipietro, Michael

Three new BODIPY dyes have been synthesized by a two-step synthetic route. Here, this expands the series to nine different BODIPY dyes by this method. Naphtha[1,2-c]pyrrole was combined with 1-pyrenecarboxaldehyde to give a symmetric dipyrrin followed by reaction with boron trifluoride to give a symmetric highly conjugated BODIPY dye. Expanding this synthetic route to a more conjugated pyrrole fluorantho[2,3-c]pyrrole was combined with 1-pyrenecarboxaldehyde followed by reaction with boron trifluoride to give the asymmetric BODIPY dye (9). Dyes with the more highly conjugated fluoranthopyrrole resulted in a bathochromic shift of ca. 50 nm in the electronic absorption and showed greater stabilitymore » of the LUMO energy, as determined by electrochemical measurements, compared to their naphthapyrrole analogs. All of the dyes synthesized by this method display molar absorptivities greater than 100 000 M -1 cm -1 with photoluminescence quantum efficiencies of 0.8–1.0. Excited state lifetimes of the dyes in dichloromethane are modest, ranging from 3.2 ns to 4.3 ns.« less

Tuning the photophysical properties of BODIPY dyes through extended aromatic pyrroles

DOE PAGES

Swavey, Shawn; Quinn, John; Coladipietro, Michael; ...

2016-12-22

Three new BODIPY dyes have been synthesized by a two-step synthetic route. Here, this expands the series to nine different BODIPY dyes by this method. Naphtha[1,2-c]pyrrole was combined with 1-pyrenecarboxaldehyde to give a symmetric dipyrrin followed by reaction with boron trifluoride to give a symmetric highly conjugated BODIPY dye. Expanding this synthetic route to a more conjugated pyrrole fluorantho[2,3-c]pyrrole was combined with 1-pyrenecarboxaldehyde followed by reaction with boron trifluoride to give the asymmetric BODIPY dye (9). Dyes with the more highly conjugated fluoranthopyrrole resulted in a bathochromic shift of ca. 50 nm in the electronic absorption and showed greater stabilitymore » of the LUMO energy, as determined by electrochemical measurements, compared to their naphthapyrrole analogs. All of the dyes synthesized by this method display molar absorptivities greater than 100 000 M -1 cm -1 with photoluminescence quantum efficiencies of 0.8–1.0. Excited state lifetimes of the dyes in dichloromethane are modest, ranging from 3.2 ns to 4.3 ns.« less

Optoelectronic and photoacoustic studies of an organic dye synthesized through green route

NASA Astrophysics Data System (ADS)

Vijayakumar, S.; Sreelatha, S.; Hatamimoslehabadi, M.; Yelleswarappu, C. S.

2017-10-01

An azo dye was prepared through an environmentally benign and economically feasible synthesis route with cardanol as a starting material. Cardanol is a cost-effective and renewable natural source obtained from Cashew Nut Shell Liquid, a by-product of the cashew industry. The dye was spectrally characterized by IR, UV-Vis, NMR and fluorescence studies. UV-Vis absorption showed a bathochromic shift between solvents of lower and higher polarities. Nonlinear optical and photoacoustic properties were studied using a frequency doubled Nd:YAG laser producing 532 nm laser pulses of 3 ns pulse width. Results show that the nonlinear absorption coefficient decreases with the increase of on-axis intensity, suggesting excited state absorption as the principal mechanism. The observed nonlinearity has applications in optoelectronics.

Fundamental characteristics of degradation-recoverable solid-state DFB polymer laser.

PubMed

Yoshioka, Hiroaki; Yang, Yu; Watanabe, Hirofumi; Oki, Yuji

2012-02-13

A novel solid-state dye laser with degradation recovery was proposed and demonstrated. Polydimethylsiloxane was used as a nanoporous solid matrix to enable the internal circulation of dye molecules in the solid state. An internal circulation model for the dye molecules was also proposed and verified numerically by assuming molecular mobility and using a proposed diffusion equation. The durability of the laser was increased 20.5-fold compared with that of a conventional polymethylmethacrylate laser. This novel laser solves the low-durability problem of dye-doped polymer lasers.

Combinatorial effects of charge characteristics and hydrophobicity of silk fibroin on the sorption and release of charged dyes.

PubMed

Wongpanit, Panya; Rujiravanit, Ratana

2012-01-01

The present study was designed to examine the influence of the charge characteristics of silk fibroin on the sorption and release of charged dyes by varying the pH values of the sorption and release media as well as types of charged dyes. Negatively charged dyes (phenol red and chromotrope 2R) and positively charged dyes (crystal violet and indoine blue) were used as the model compounds. Silk fibroin films were prepared by using a solution casting technique. The prepared films were then treated with an aqueous methanol solution or annealed with water to control their conformation. The sorption behavior of the model compounds made by the methanol-treated and water-annealed silk fibroin films was investigated. Compared to the water- annealed silk fibroin films, a higher hydrophobicity of the methanol-treated silk fibroin films caused a higher sorption of the hydrophobic dyes. The dye molecules had a fairly high affinity to the silk fibroin film, even though the dye and the matrix possessed the same charge. However, in the presence of two charged groups in a single dye molecule, the electrostatic repulsion become more dominant. Stronger interaction was observed when the charges of the film and the dye were opposite. The results of dye sorption and release experiments showed that the degree of synergism or competition between electrostatic and hydrophobic interactions directly depended on the charges and chemical structure of the dye molecules and the environmental pH conditions of the existing silk fibroin film.

EXAFS, ab Initio Molecular Dynamics, and NICIS Spectroscopy Studies on an Organic Dye Model at the Dye-Sensitized Solar Cell Photoelectrode Interface.

PubMed

Liu, Peng; Johansson, Viktor; Trilaksana, Herri; Rosdahl, Jan; Andersson, Gunther G; Kloo, Lars

2017-06-14

The organization of dye molecules in the dye layer adsorbed on the semiconductor substrate in dye-sensitized solar cells has been studied using a combination of theoretical methods and experimental techniques. The model system is based on the simple D-π-A dye L0, which has been chemically modified by substituting the acceptor group CN with Br (L0Br) to offer better X-ray contrast. Experimental EXAFS data based on the Br K-edge backscattering show no obvious difference between dye-sensitized titania powder and titania film samples, thus allowing model systems to be based on powder slurries. Ab initio molecular dynamic (aiMD) calculations have been performed to extract less biased information from the experimental EXASF data. Using the aiMD calculation as input, the EXAFS structural models can be generated a priori that match the experimental data. Our study shows that the L0Br dye adsorbs in the trans-L0Br configuration and that adsorption involves both a proximity to other L0Br dye molecules and the titanium atoms in the TiO 2 substrate. These results indicate direct coordination of the dye molecules to the TiO 2 surface in contrast to previous results on metal-organic dyes. The molecular coverage of L0Br on mesoporous TiO 2 was also estimated using NICIS spectroscopy. The NICISS results emphasized that the L0Br dye on nanoporous titania mainly forms monolayers with a small contribution of multilayer coverage.

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.

3D Oxidized Graphene Frameworks: An Efficient Adsorbent for Methylene Blue

NASA Astrophysics Data System (ADS)

Pandey, Abhishek; Deb, Madhurima; Tiwari, Shreya; Pawar, Pranav Bhagwan; Saxena, Sumit; Shukla, Shobha

2018-04-01

Extraordinary properties of graphene and its derivatives have found application in varied areas such as energy, electronics, optical devices and sensors, to name a few. Large surface area along with specialized functional groups make these materials attractive for removal of dye molecules in solution via adsorption. Industrial effluents contain large amounts of toxic chemicals resulting in pollution of water bodies, which pose environmental hazards in general. Here we report application of 3D oxidized graphene frameworks in the efficient removal of cationic dye molecules such as methylene blue via adsorption. Systematic parametric studies investigating the effect of the initial dye concentration, pH and contact time have been performed. Spectroscopic analysis of the filtrate suggests that tortuous paths in 3D oxidized graphene frameworks result in efficient removal of dye molecules due to enhanced interaction. The hydroxyl groups retained in these 3D oxidized graphene frameworks facilitate adsorption of the dye molecules while passing through the adsorbent. pH studies suggest that maximum removal efficiency for methylene blue was achieved at pH value of 9. The results suggest that these 3D oxidized graphene frameworks can be used for purification of large volumes of contaminated water from cationic dyes in waste water treatment plants.

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.

Insights into the Mechanism of a Covalently Linked Organic Dye–Cobaloxime Catalyst System for Dye‐Sensitized Solar Fuel Devices

PubMed Central

Pati, Palas Baran; Zhang, Lei; Philippe, Bertrand; Fernández‐Terán, Ricardo; Ahmadi, Sareh; Tian, Lei; Rensmo, Håkan; Hammarström, Leif

2017-01-01

Abstract A covalently linked organic dye–cobaloxime catalyst system based on mesoporous NiO is synthesized by a facile click reaction for mechanistic studies and application in a dye‐sensitized solar fuel device. The system is systematically investigated by photoelectrochemical measurements, density functional theory, time‐resolved fluorescence, transient absorption spectroscopy, and photoelectron spectroscopy. The results show that irradiation of the dye–catalyst on NiO leads to ultrafast hole injection into NiO from the excited dye, followed by a fast electron transfer process to reduce the catalyst. Moreover, the dye adopts different structures with different excited state energies, and excitation energy transfer occurs between neighboring molecules on the semiconductor surface. The photoelectrochemical experiments also show hydrogen production by this system. The axial chloride ligands of the catalyst are released during photocatalysis to create the active sites for proton reduction. A working mechanism of the dye–catalyst system on the photocathode is proposed on the basis of this study. PMID:28338295

Improving Light Harvesting in Dye-Sensitized Solar Cells Using Hybrid Bimetallic Nanostructures

DOE PAGES

Zarick, Holly F.; Erwin, William R.; Boulesbaa, Abdelaziz; ...

2016-01-25

In this paper, we demonstrate improved light trapping in dye-sensitized solar cells (DSSCs) with hybrid bimetallic gold core/silver shell nanostructures. Silica-coated bimetallic nanostructures (Au/Ag/SiO 2 NSs) integrated in the active layer of DSSCs resulted in 7.51% power conversion efficiency relative to 5.97% for reference DSSCs, giving rise to 26% enhancement in device performance. DSSC efficiencies were governed by the particle density of Au/Ag/SiO 2 NSs with best performing devices utilizing only 0.44 wt % of nanostructures. We performed transient absorption spectroscopy of DSSCs with variable concentrations of Au/Ag/SiO 2 NSs and observed an increase in amplitude and decrease in lifetimemore » with increasing particle density relative to reference. Finally, we attributed this trend to plasmon resonant energy transfer and population of the singlet excited states of the sensitizer molecules at the optimum concentration of NSs promoting enhanced exciton generation and rapid charge transfer into TiO 2.« less

How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

PubMed Central

Vaissier, Valerie; Sakai, Victoria Garcia; Li, Xiaoe; Cabral, João T.; Nelson, Jenny; Barnes, Piers R. F.

2016-01-01

Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results. PMID:27991538

How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

NASA Astrophysics Data System (ADS)

Vaissier, Valerie; Sakai, Victoria Garcia; Li, Xiaoe; Cabral, João T.; Nelson, Jenny; Barnes, Piers R. F.

2016-12-01

Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results.

Organic photosensitizers with a heteroleptic dual donor for dye-sensitized solar cells.

PubMed

Kim, Joo Young; Kim, Young Sik

2012-04-01

Using DFT and TDDFT calculations, we investigated the substitution effect in the electronic and optical properties of dye sensitizers with a dual donor composed of triphenylamine and/or indoline moieties. Due to replacement with the dual donor moieties, the HOMO levels were split into HOMO and HOMO - 1 levels, and the bandgaps between the HOMO and LUMO levels decreased, leading to the creation of bathochromically extended absorption spectra. Nearly degenerated splitting of the HOMO levels resulted from the similarity of the electronic structure between the HOMO and the HOMO - 1 levels, delocalized over both dual-donor moieties, when replacing the dual donors. It was shown that the additional electron-donating group creates an additional absorption band and causes a cascading two-electron process aiding the charge separation process. Owing to a more panchromatic attribute, easier energy transfer and feasible retardation of the recombination between the injected electrons and the electrolyte, it is expected that dyeTI will show better performance than the other dyes (dyeT dyeTT and dyeIT) as denoted here in terms of the conversion efficiency of dye-sensitized solar cells (DSSCs). This work presents the probable benefits of dye sensitizers with dual-donor moieties and provides insight into the development of more efficient dye sensitizers for DSSCs through modification of the Frontier molecular orbitals.

Simultaneous measurements of absorption spectrum and refractive index in a microfluidic system.

PubMed

Helseth, Lars Egil

2012-02-13

The characterization of dyes in various solvents requires determination of the absorption spectrum of the dye as well as the refractive index of the solvent. Typically, the refractive index of the solvent and the absorption spectrum of the solute are measured using separate experimental setups where significant liquid volumes are required. In this work the first optical measurement system that is able to do simultaneous measurements of the refractive index of the solvent and the spectral properties of the solute in a microscopic volume is presented. The laser dye Rhodamine 6G in glycerol is investigated, and the refractive index of the solution is monitored using the interference pattern of the light scattered off the channel, while its spectral properties is found by monitoring reflected light from the channel.

Structural Information from Single-molecule FRET Experiments Using the Fast Nano-positioning System

PubMed Central

Röcker, Carlheinz; Nagy, Julia; Michaelis, Jens

2017-01-01

Single-molecule Förster Resonance Energy Transfer (smFRET) can be used to obtain structural information on biomolecular complexes in real-time. Thereby, multiple smFRET measurements are used to localize an unknown dye position inside a protein complex by means of trilateration. In order to obtain quantitative information, the Nano-Positioning System (NPS) uses probabilistic data analysis to combine structural information from X-ray crystallography with single-molecule fluorescence data to calculate not only the most probable position but the complete three-dimensional probability distribution, termed posterior, which indicates the experimental uncertainty. The concept was generalized for the analysis of smFRET networks containing numerous dye molecules. The latest version of NPS, Fast-NPS, features a new algorithm using Bayesian parameter estimation based on Markov Chain Monte Carlo sampling and parallel tempering that allows for the analysis of large smFRET networks in a comparably short time. Moreover, Fast-NPS allows the calculation of the posterior by choosing one of five different models for each dye, that account for the different spatial and orientational behavior exhibited by the dye molecules due to their local environment. Here we present a detailed protocol for obtaining smFRET data and applying the Fast-NPS. We provide detailed instructions for the acquisition of the three input parameters of Fast-NPS: the smFRET values, as well as the quantum yield and anisotropy of the dye molecules. Recently, the NPS has been used to elucidate the architecture of an archaeal open promotor complex. This data is used to demonstrate the influence of the five different dye models on the posterior distribution. PMID:28287526

Structural Information from Single-molecule FRET Experiments Using the Fast Nano-positioning System.

PubMed

Dörfler, Thilo; Eilert, Tobias; Röcker, Carlheinz; Nagy, Julia; Michaelis, Jens

2017-02-09

Single-molecule Förster Resonance Energy Transfer (smFRET) can be used to obtain structural information on biomolecular complexes in real-time. Thereby, multiple smFRET measurements are used to localize an unknown dye position inside a protein complex by means of trilateration. In order to obtain quantitative information, the Nano-Positioning System (NPS) uses probabilistic data analysis to combine structural information from X-ray crystallography with single-molecule fluorescence data to calculate not only the most probable position but the complete three-dimensional probability distribution, termed posterior, which indicates the experimental uncertainty. The concept was generalized for the analysis of smFRET networks containing numerous dye molecules. The latest version of NPS, Fast-NPS, features a new algorithm using Bayesian parameter estimation based on Markov Chain Monte Carlo sampling and parallel tempering that allows for the analysis of large smFRET networks in a comparably short time. Moreover, Fast-NPS allows the calculation of the posterior by choosing one of five different models for each dye, that account for the different spatial and orientational behavior exhibited by the dye molecules due to their local environment. Here we present a detailed protocol for obtaining smFRET data and applying the Fast-NPS. We provide detailed instructions for the acquisition of the three input parameters of Fast-NPS: the smFRET values, as well as the quantum yield and anisotropy of the dye molecules. Recently, the NPS has been used to elucidate the architecture of an archaeal open promotor complex. This data is used to demonstrate the influence of the five different dye models on the posterior distribution.

[Spectral and fluorescent study of the interaction of squarylium dyes, derivatives of 3H-indolium, with albumins].

PubMed

Tatikolov, A S; Panova, I G; Ishchenko, A A; Kudinova, M A

2010-01-01

Noncovalent interactions of intraionic squarylium dyes, derivatives of 3H-indolium, as well as the structurally analogous ionic indodicarbocyanine dye with serum albumins (human, bovine, rat) and, for comparison, with ovalbumin has been studied by spectral and fluorescent methods. The hydrophilic squarylium dye with sulfonate groups was found to interact with albumins more efficiently, which is probably due to the double negative charge on the dye molecule at the expense of the sulfonate groups and the ability to form hydrogen bonds with albumin. The hydrophilic indodicarbocyanine dye without the squarylium group in its structure binds to albumins much more weaker than the structurally analogous squarylium dye. The dyes bind to ovalbumin less efficiently than to serum albumins. Along with the binding of monomeric dye molecules, the aggregation of the dyes on albumins is also observed. The hydrophobic squarylium dye without sulfonate groups tends to form aggregates in aqueous solutions, which partially decompose upon the introduction of albumin into the solution. The hydrophilic squarylium dye with sulfonate groups can be recommended for tests as a spectral-fluorescent probe for serum albumins in extracellular media of living organisms.

Charge transfer optical absorption and fluorescence emission of 4-(9-acridyl)julolidine from long-range-corrected time dependent density functional theory in polarizable continuum approach.

PubMed

Kityk, A V

2014-07-15

A long-range-corrected time-dependent density functional theory (LC-TDDFT) in combination with polarizable continuum model (PCM) have been applied to study charge transfer (CT) optical absorption and fluorescence emission energies basing on parameterized LC-BLYP xc-potential. The molecule of 4-(9-acridyl)julolidine selected for this study represents typical CT donor-acceptor dye with strongly solvent dependent optical absorption and fluorescence emission spectra. The result of calculations are compared with experimental spectra reported in the literature to derive an optimal value of the model screening parameter ω. The first absorption band appears to be quite well predictable within DFT/TDDFT/PCM with the screening parameter ω to be solvent independent (ω ≈ 0.245 Bohr(-1)) whereas the fluorescence emission exhibits a strong dependence on the range separation with ω-value varying on a rising solvent polarity from about 0.225 to 0.151 Bohr(-1). Dipolar properties of the initial state participating in the electronic transition have crucial impact on the effective screening. Copyright © 2014 Elsevier B.V. All rights reserved.

Albumin binds self-assembling dyes as specific polymolecular ligands.

PubMed

Stopa, Barbara; Rybarska, Janina; Drozd, Anna; Konieczny, Leszek; Król, Marcin; Lisowski, Marek; Piekarska, Barbara; Roterman, Irena; Spólnik, Paweł; Zemanek, Grzegorz

2006-12-15

Self-assembling dyes with a structure related to Congo red (e.g. Evans blue) form polymolecular complexes with albumin. The dyes, which are lacking a self-assembling property (Trypan blue, ANS) bind as single molecules. The supramolecular character of dye ligands bound to albumin was demonstrated by indicating the complexation of dye molecules outnumbering the binding sites in albumin and by measuring the hydrodynamic radius of albumin which is growing upon complexation of self-assembling dye in contrast to dyes lacking this property. The self-assembled character of Congo red was also proved using it as a carrier introducing to albumin the intercalated nonbonding foreign compounds. Supramolecular, ordered character of the dye in the complex with albumin was also revealed by finding that self-assembling dyes become chiral upon complexation. Congo red complexation makes albumin less resistant to low pH as concluded from the facilitated N-F transition, observed in studies based on the measurement of hydrodynamic radius. This particular interference with protein stability and the specific changes in digestion resulted from binding of Congo red suggest that the self-assembled dye penetrates the central crevice of albumin.

Photoinduced electron transfer of oxazine 1/TiO2 nanoparticles at single molecule level by using confocal fluorescence microscopy.

PubMed

Chen, Yi-Ju; Tzeng, Hsin-Yu; Fan, Hsiu-Fang; Chen, Ming-Shiang; Huang, Jer-Shing; Lin, King-Chuen

2010-06-01

Kinetics of photoinduced electron transfer (ET) from oxazine 1 dye to TiO(2) nanoparticles (NPs) surface is studied at a single molecule level by using confocal fluorescence microscopy. Upon irradiation with a pulsed laser at 630 nm, the fluorescence lifetimes sampled among 100 different dye molecules are determined to yield an average lifetime of 2.9 +/- 0.3 ns, which is close to the value of 3.0 +/- 0.6 ns measured on the bare coverslip. The lifetime proximity suggests that most interfacial electron transfer (IFET) processes for the current system are inefficient, probably caused by physisorption between dye and the TiO(2) film. However, there might exist some molecules which are quenched before fluorescing and fail to be detected. With the aid of autocorrelation analysis under a three-level energy system, the IFET kinetics of single dye molecules in the conduction band of TiO(2) NPs is evaluated to be (1.0 +/- 0.1) x 10(4) s(-1) averaged over 100 single molecules and the back ET rate constant is 4.7 +/- 0.9 s(-1). When a thicker TiO(2) film is substituted, the resultant kinetic data do not make a significant difference. The trend of IFET efficacy agrees with the method of fluorescence lifetime measurements. The obtained forward ET rate constants are about ten times smaller than the photovoltage response measured in an assembled dye-sensitized solar cell. The discrepancy is discussed. The inhomogeneous and fluctuation characters for the IFET process are attributed to microenvironment variation for each single molecule. The obtained ET rates are much slower than the fluorescence relaxation. Such a small ET quantum yield is yet feasibly detectable at a single molecule level.

Fluorescence of acridinic dyes in anionic surfactant solution

NASA Astrophysics Data System (ADS)

Pereira, Robson Valentim; Gehlen, Marcelo Henrique

2005-10-01

The interaction of the cationic dyes acridine, 9-aminoacridine (9AA), and proflavine, with sodium dodecyl sulfate (SDS) was studied by electronic absorption, steady-state and time-resolved fluorescence spectroscopies. The dyes interact with SDS in the pre-micellar region leading in two cases to dimerization in dye-surfactant aggregates, but with distinct molecular arrangements. For proflavine, the observed red shift of the electronic absorption band indicates the presence of J-aggregate, which are nonfluorescent. In the case of 9AA, the aggregates were characterized as nonspecific (neither J- nor H-type is spectroscopically observed). The time-resolved emission spectra gives evidences of the presence of weakly bound dimers by the recovery of three defined decay times by global analysis: dye monomer ( τ1 = 16.4 ns), dimer ( τ2 = 7.1 ns), and a faster component ( τ3 = 2.1 ns) ascribed to intracluster energy migration between monomer and dimer. Acridine has a weak interaction with SDS forming only an ion pair without further self-aggregation of the dye.

Fluorescence of acridinic dyes in anionic surfactant solution.

PubMed

Pereira, Robson Valentim; Gehlen, Marcelo Henrique

2005-10-01

The interaction of the cationic dyes acridine, 9-aminoacridine (9AA), and proflavine, with sodium dodecyl sulfate (SDS) was studied by electronic absorption, steady-state and time-resolved fluorescence spectroscopies. The dyes interact with SDS in the pre-micellar region leading in two cases to dimerization in dye-surfactant aggregates, but with distinct molecular arrangements. For proflavine, the observed red shift of the electronic absorption band indicates the presence of J-aggregate, which are nonfluorescent. In the case of 9AA, the aggregates were characterized as nonspecific (neither J- nor H-type is spectroscopically observed). The time-resolved emission spectra gives evidences of the presence of weakly bound dimers by the recovery of three defined decay times by global analysis: dye monomer (tau1 = 16.4 ns), dimer (tau2 = 7.1 ns), and a faster component (tau3 = 2.1 ns) ascribed to intracluster energy migration between monomer and dimer. Acridine has a weak interaction with SDS forming only an ion pair without further self-aggregation of the dye.

A Brief Account of Nanoparticle Contrast Agents for Photoacoustic Imaging

PubMed Central

Pan, Dipanjan; Kim, Benjamin; Wang, Lihong V.; Lanza, Gregory M

2014-01-01

Photoacoustic imaging (PAI) is a hybrid, nonionizing modality offering excellent spatial resolution, deep penetration, and high soft tissue contrast. In PAI, signal is generated based on the absorption of laser-generated optical energy by endogenous tissues or exogenous contrast agents leading to acoustic emissions detected by an ultrasound transducer. Research in this area over the years has shown that PAI has the ability to provide both physiological and molecular imaging, which can be viewed alone or used in a hybrid modality fashion to extend the anatomic and hemodynamic sensitivities of clinical ultrasound. PAI may be performed using inherent contrast afforded by light absorbing molecules such as hemoglobin, myoglobin, and melanin or exogenous small molecule contrast agent such as near infrared dyes and porphyrins. However, this review summarizes the potential of exogenous nanoparticle-based agents for PAI applications including contrast based on gold particles, carbon nanotubes, and encapsulated copper compounds. PMID:23983210

Molecular structure and spectroscopic investigation of sodium(E)-2-hydroxy-5-((4-sulfonatophenyl)diazenyl)benzoate: A DFT study

NASA Astrophysics Data System (ADS)

Shahab, Siyamak; Kumar, Rakesh; Darroudi, Mahdieh; Yousefzadeh Borzehandani, Mostafa

2015-03-01

Quantum-chemical calculations using the Density Functional Theory (DFT) approach for structural analysis of new azodye sodium(E)-2-hydroxy-5-((4-sulfonatophenyl)diazenyl) (trans isomer) is carried out using B3LYP methods with 6-31G∗ basis set. The comparison of measured UV-Vis data, IR and NMR spectra of the molecule with the experimental data were also described which allowed assignment of major spectral features of title molecule. The optimized geometrical parameters obtained by B3LYP methods show a good agreement with experimental data. On the basis of polyvinyl alcohol (PVA) and the dichroic synthesized dye polarizer absorbing in the UV region of the spectrum (λmax = 353 nm) with the effect of polarization in the absorption maximum 96% was developed. The spectral-polarization parameters of stretched PVA-films were calculated.

Experimental Resonance Enhanced Multiphoton Ionization (REMPI) studies of small molecules

NASA Technical Reports Server (NTRS)

Dehmer, J. L.; Dehmer, P. M.; Pratt, S. T.; Ohalloran, M. A.; Tomkins, F. S.

1987-01-01

Resonance enhanced multiphoton ionization (REMPI) utilizes tunable dye lasers to ionize an atom or molecule by first preparing an excited state by multiphoton absorption and then ionizing that state before it can decay. This process is highly selective with respect to both the initial and resonant intermediate states of the target, and it can be extremely sensitive. In addition, the products of the REMPI process can be detected as needed by analyzing the resulting electrons, ions, fluorescence, or by additional REMPI. This points to a number of exciting opportunities for both basic and applied science. On the applied side, REMPI has great potential as an ultrasensitive, highly selective detector for trace, reactive, or transient species. On the basic side, REMPI affords an unprecedented means of exploring excited state physics and chemistry at the quantum-state-specific level. An overview of current studies of excited molecular states is given to illustrate the principles and prospects of REMPI.

Exciplex emission from a boron dipyrromethene (Bodipy) dye equipped with a dicyanovinyl appendage.

PubMed

Nano, Adela; Ziessel, Raymond; Stachelek, Patrycja; Alamiry, Mohammed A H; Harriman, Anthony

2014-01-13

The photophysical properties of a prototypic donor-acceptor dyad, featuring a conventional boron dipyrromethene (Bodipy) dye linked to a dicyanovinyl unit through a meso-phenylene ring, have been recorded in weakly polar solvents. The absorption spectrum remains unperturbed relative to that of the parent Bodipy dye but the fluorescence is extensively quenched. At room temperature, the emission spectrum comprises roughly equal contributions from the regular π, π* excited-singlet state and from an exciplex formed by partial charge transfer from Bodipy to the dicyanovinyl residue. This mixture moves progressively in favor of the locally excited π, π* state on cooling and the exciplex is no longer seen in frozen media; the overall emission quantum yield changes dramatically near the freezing point of the solvent. The exciplex, which has a lifetime of approximately 1 ns at room temperature, can also be seen by transient absorption spectroscopy, in which it decays to form the locally excited triplet state. Under applied pressure (P<170 MPa), formation of the exciplex is somewhat hindered by restricted rotation around the semirigid linkage and again the emission profile shifts in favor of the π, π* excited state. At higher pressure (170

Photophysical parameters and fluorescence quenching of 7-diethylaminocoumarin (DEAC) laser dye

NASA Astrophysics Data System (ADS)

El-Mossalamy, E. H.; Obaid, A. Y.; El-Daly, S. A.

2011-10-01

The optical properties including electronic absorption spectrum, emission spectrum, fluorescence quantum yield, and dipole moment of electronic transition of 7-diethylaminocoumarin (DEAC) laser dye have been measured in different solvents. Both electronic absorption and fluorescence spectra are red shifted as the polarity of the medium increases, indicating that the dipole moment of molecule increases on excitation. The fluorescence quantum yield of DEAC decreases as the polarity of solvent increases, a result of the role of solvent polarity in stabilization of the twisting of the intramolecular charge transfer (TICT) in excited state, which is a non-emissive state, as well as hydrogen bonding with the hetero-atom of dye. The emission spectrum of DEAC has also been measured in cationic (CTAC) and anionic (SDS) micelles, the intensity increases as the concentration of surfactant increases, and an abrupt change in emission intensity is observed at critical micelle concentration (CMC) of surfactant. 2×10 -3 mol dm -3 of DEAC gives laser emission in the blue region on pumping with nitrogen laser ( λex=337.1 nm). The laser parameters such as tuning range, gain coefficient ( α), emission cross section ( σe), and half-life energy have been calculated in different solvents, namely acetone, dioxane , ethanol, and dimethyforamide (DMF). The photoreactivity of DEAC has been studied in CCl 4 at a wavelength of 366 nm. The values of photochemical yield ( ϕc) and rate constant ( k) are determined. The interaction of organic acceptors such as picric acid (PA), tetracyanoethylene (TCNE), and 7,7,8,8-tetracynoquinonedimethane (TCNQ) with DEAC is also studied using fluorescence measurements in acetonitrile (CH 3CN); from fluorescence quenching study we assume the possible electron transfer from excited donor DEAC to organic acceptor forming non-emissive exciplex.

Reichardt's dye and its reactions with the alkylating agents 4-chloro-1-butanol, ethyl methanesulfonate, 1-bromobutane and Fast Red B - a potentially useful reagent for the detection of genotoxic impurities in pharmaceuticals.

PubMed

Corrigan, Damion K; Whitcombe, Michael J; McCrossen, Sean; Piletsky, Sergey

2009-04-01

Alkylating agents are potentially genotoxic impurities that may be present in drug products. These impurities occur in pharmaceuticals as by-products from the synthetic steps involved in drug production, as impurities in starting materials or from in-situ reactions that take place in the final drug product. Currently, analysis for genotoxic impurities is typically carried out using either HPLC/MS or GC/MS. These techniques require specialist expertise, have long analysis times and often use sample clean-up procedures. Reichardt's dye is well known for its solvatochromic properties. In this paper the dye's ability to undergo alkylation is reported. The reaction between Reichardt's dye and alkylating agents such as 4-chloro-1-butanol and ethyl methanesulfonate was monitored spectrophotometrically at 618 nm in acetonitrile and 624 nm in N,N-dimethylformamide. Changes in absorption were observed using low levels of alkylating agent (5-10 parts per million). Alkylation of the dye with 4-chloro-1-butanol and ethyl methanesulfonate was confirmed. Reichardt's dye, and its changing UV absorption, was examined in the presence of paracetamol (10 and 100 mg/ml). Whilst the alkylation-induced changes in UV absorption were not as pronounced as with standard solutions, detection of alkylation was still possible. Using standard solutions and in the presence of a drug matrix, Reichardt's dye shows promise as a reagent for detection of low levels of industrially important alkylating agents.

Staining Method for Protein Analysis by Capillary Gel Electrophoresis

PubMed Central

Wu, Shuqing; Lu, Joann J; Wang, Shili; Peck, Kristy L.; Li, Guigen; Liu, Shaorong

2009-01-01

A novel staining method and the associated fluorescent dye were developed for protein analysis by capillary SDS-PAGE. The method strategy is to synthesize a pseudo-SDS dye and use it to replace some of the SDS in SDS–protein complexes so that the protein can be fluorescently detected. The pseudo-SDS dye consists of a long, straight alkyl chain connected to a negative charged fluorescent head and binds to proteins just as SDS. The number of dye molecules incorporated with a protein depends on the dye concentration relative to SDS in the sample solution, since SDS and dye bind to proteins competitively. In this work, we synthesized a series of pseudo-SDS dyes, and tested their performances for capillary SDS-PAGE. FT-16 (a fluorescein molecule linked with a hexadodecyl group) seemed to be the best among all the dyes tested. Although the numbers of dye molecules bound to proteins (and the fluorescence signals from these protein complexes) were maximized in the absence of SDS, high-quality separations were obtained when co-complexes of SDS–protein–dye were formed. The migration time correlates well with protein size even after some of the SDS in the SDS–protein complexes was replaced by the pseudo-SDS dye. Under optimized experimental conditions and using a laser-induced fluorescence detector, limits of detection of as low as 0.13 ng/mL (bovine serum albumin) and dynamic ranges over 5 orders of magnitude in which fluorescence response is proportional to the square root of analyte concentration were obtained. The method and dye were also tested for separations of real-world samples from E. coli. PMID:17874848

Laser performance of Coumarin 540A dye molecules in polymeric host media with different viscosities: From liquid solution to solid polymer matrix

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

Costela, A.; Garcia-Moreno, I.; Barroso, J.

1998-01-01

Photophysical parameters and lasing properties of Coumarin 540A dye molecules are studied in solutions of increasing viscosity, from liquid solutions in 1,4-dioxane to solid solutions in poly(methyl methacrylate). The fluorescence quantum yield and lasing efficiencies decrease as the viscosity of the solution increases, reflecting the strong influence of the rigidity of the medium on the radiative processes. The photodegradation mechanisms acting on the fluorophores are analyzed by following the dependence of laser induced fluorescence and laser output on the number of pump laser pulses. The fluorescence redistribution after pattern photobleaching technique is used, and Fick{close_quote}s second law is applied tomore » study the diffusion of dye molecules in the highly viscous polymer solutions. The diffusion coefficients of the dye molecules as a function of the increased viscosity of the medium are determined. {copyright} {ital 1998 American Institute of Physics.}« less

Peptide-based ambidextrous bifunctional gelator: applications in oil spill recovery and removal of toxic organic dyes for waste water management.

PubMed

Basu, Kingshuk; Nandi, Nibedita; Mondal, Biplab; Dehsorkhi, Ashkan; Hamley, Ian W; Banerjee, Arindam

2017-12-06

A low molecular weight peptide-based ambidextrous gelator molecule has been discovered for efficient control of water pollution. The gelator molecules can gel various organic solvents with diverse polarity, e.g. n -hexane, n -octane, petroleum ether, petrol, diesel, aromatic solvents like chlorobenzene, toluene, benzene, o -xylene and even aqueous phosphate buffer of pH 7.5. These gels have been thoroughly characterized using various techniques including field emission scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray powder diffraction analysis, small angle X-ray scattering and rheological experiments. Interestingly, hydrogel obtained from the gelator molecule has been found to absorb toxic organic dyes (both cationic and anionic dyes) from dye-contaminated water. The gelator molecule can be reused for several cycles, indicating its possible future use in waste water management. Moreover, this gelator can selectively gel petrol, diesel, pump oil from an oil-water mixture in the presence of a carrier solvent, ethyl acetate, suggesting its efficient application for oil spill recovery. These results indicate that the peptide-based ambidextrous gelator produces soft materials (gels) with dual function: (i) removal of toxic organic dyes in waste water treatment and (ii) oil spill recovery.

Photoactive dye-enhanced tissue ablation for endoscopic laser prostatectomy.

PubMed

Ahn, Minwoo; Hau, Nguyen Trung; Van Phuc, Nguyen; Oh, Junghwan; Kang, Hyun Wook

2014-11-01

Laser light has been widely used as a surgical tool to treat benign prostate hyperplasia (BPH) over 20 years. Recently, application of high laser power up to 200 W was often reported to swiftly remove a large amount of prostatic tissue. The purpose of this study was to validate the feasibility of photoactive dye injection to enhance light absorption and eventually to facilitate tissue vaporization with low laser power. Chicken breast tissue was selected as a target tissue due to minimal optical absorption at the visible wavelength. Four biocompatible photoactive dyes, including amaranth (AR), black dye (BD), hemoglobin powder (HP), and endoscopic marker (EM), were selected and tested in vitro with a customized 532 nm laser system with radiant exposure ranging from 0.9 to 3.9 J/cm(2) . Light absorbance and ablation threshold were measured with UV-Vis spectrometer and Probit analysis, respectively, and compared to feature the function of the injected dyes. Ablation performance with dye-injection was evaluated in light of radiant exposure, dye concentration, and number of injection. Higher light absorption by injected dyes led to lower ablation threshold as well as more efficient tissue removal in the order of AR, BD, HP, and EM. Regardless of the injected dyes, ablation efficiency principally increased with radiant exposure, dye concentration, and number of injection. Among the dyes, AR created the highest ablation rate of 44.2 ± 0.2 µm/pulse due to higher absorbance and lower ablation threshold. High aspect ratios up to 7.1 ± 0.4 entailed saturation behavior in the tissue ablation injected with AR and BD, possibly resulting from plume shielding and increased scattering due to coagulation. Preliminary tests on canine prostate with a hydraulic injection system demonstrated that 80 W with dye injection yielded comparable ablation efficiency to 120 W with no injection, indicating 33% reduced laser power with almost equivalent performance. Due to efficient coupling of optical energy, pre-injection of photoactive dyes promoted the degree of tissue removal during laser irradiation. Further studies will investigate spatial distribution of dyes and optimal injecting pressure to govern the extent of dye-assisted ablation in a predictable manner. In-depth comprehension on photoactive dye-enhanced tissue ablation can help accomplish efficient and safe laser vaporization for BPH with low power application. © 2014 Wiley Periodicals, Inc.

Reconstruction of calmodulin single-molecule FRET states, dye interactions, and CaMKII peptide binding by MultiNest and classic maximum entropy

NASA Astrophysics Data System (ADS)

DeVore, Matthew S.; Gull, Stephen F.; Johnson, Carey K.

2013-08-01

We analyzed single molecule FRET burst measurements using Bayesian nested sampling. The MultiNest algorithm produces accurate FRET efficiency distributions from single-molecule data. FRET efficiency distributions recovered by MultiNest and classic maximum entropy are compared for simulated data and for calmodulin labeled at residues 44 and 117. MultiNest compares favorably with maximum entropy analysis for simulated data, judged by the Bayesian evidence. FRET efficiency distributions recovered for calmodulin labeled with two different FRET dye pairs depended on the dye pair and changed upon Ca2+ binding. We also looked at the FRET efficiency distributions of calmodulin bound to the calcium/calmodulin dependent protein kinase II (CaMKII) binding domain. For both dye pairs, the FRET efficiency distribution collapsed to a single peak in the case of calmodulin bound to the CaMKII peptide. These measurements strongly suggest that consideration of dye-protein interactions is crucial in forming an accurate picture of protein conformations from FRET data.

Reconstruction of Calmodulin Single-Molecule FRET States, Dye-Interactions, and CaMKII Peptide Binding by MultiNest and Classic Maximum Entropy

PubMed Central

DeVore, Matthew S.; Gull, Stephen F.; Johnson, Carey K.

2013-01-01

We analyze single molecule FRET burst measurements using Bayesian nested sampling. The MultiNest algorithm produces accurate FRET efficiency distributions from single-molecule data. FRET efficiency distributions recovered by MultiNest and classic maximum entropy are compared for simulated data and for calmodulin labeled at residues 44 and 117. MultiNest compares favorably with maximum entropy analysis for simulated data, judged by the Bayesian evidence. FRET efficiency distributions recovered for calmodulin labeled with two different FRET dye pairs depended on the dye pair and changed upon Ca2+ binding. We also looked at the FRET efficiency distributions of calmodulin bound to the calcium/calmodulin dependent protein kinase II (CaMKII) binding domain. For both dye pairs, the FRET efficiency distribution collapsed to a single peak in the case of calmodulin bound to the CaMKII peptide. These measurements strongly suggest that consideration of dye-protein interactions is crucial in forming an accurate picture of protein conformations from FRET data. PMID:24223465

Reconstruction of Calmodulin Single-Molecule FRET States, Dye-Interactions, and CaMKII Peptide Binding by MultiNest and Classic Maximum Entropy.

PubMed

Devore, Matthew S; Gull, Stephen F; Johnson, Carey K

2013-08-30

We analyze single molecule FRET burst measurements using Bayesian nested sampling. The MultiNest algorithm produces accurate FRET efficiency distributions from single-molecule data. FRET efficiency distributions recovered by MultiNest and classic maximum entropy are compared for simulated data and for calmodulin labeled at residues 44 and 117. MultiNest compares favorably with maximum entropy analysis for simulated data, judged by the Bayesian evidence. FRET efficiency distributions recovered for calmodulin labeled with two different FRET dye pairs depended on the dye pair and changed upon Ca 2+ binding. We also looked at the FRET efficiency distributions of calmodulin bound to the calcium/calmodulin dependent protein kinase II (CaMKII) binding domain. For both dye pairs, the FRET efficiency distribution collapsed to a single peak in the case of calmodulin bound to the CaMKII peptide. These measurements strongly suggest that consideration of dye-protein interactions is crucial in forming an accurate picture of protein conformations from FRET data.

Enhanced electronic excitation energy transfer between dye molecules incorporated in nano-scale media with apparent fractal dimensionality

NASA Astrophysics Data System (ADS)

Yefimova, Svetlana L.; Rekalo, Andrey M.; Gnap, Bogdan A.; Viagin, Oleg G.; Sorokin, Alexander V.; Malyukin, Yuri V.

2014-09-01

In the present study, we analyze the efficiency of Electronic Excitation Energy Transfer (EEET) between two dyes, an energy donor (D) and acceptor (A), concentrated in structurally heterogeneous media (surfactant micelles, liposomes, and porous SiO2 matrices). In all three cases, highly effective EEET in pairs of dyes has been found and cannot be explained by Standard Förster-type theory for homogeneous solutions. Two independent approaches based on the analysis of either the D relative quantum yield () or the D fluorescence decay have been used to study the deviation of experimental results from the theoretical description of EEET process. The observed deviation is quantified by the apparent fractal distribution of molecules parameter . We conclude that the highly effective EEET observed in the nano-scale media under study can be explained by both forced concentration of the hydrophobic dyes within nano-volumes and non-uniform cluster-like character of the distribution of D and A dye molecules within nano-volumes.

Laboratory measurements of selected optical, physical, chemical, and remote-sensing properties of five water mixtures containing Calvert clay and a nonfluorescing dye

NASA Technical Reports Server (NTRS)

Usry, J. W.; Whitlock, C. H.; Poole, L. R.; Witte, W. G., Jr.

1981-01-01

Total suspended solids concentrations ranged from 6.1 ppm to 24.3 ppm and sizes ranged between 1.5 micrometers and 10 micrometers with the most frequently occurring size less than 2 micrometers. Iron concentration was less than 1 percent of the total suspended solids. Nonfluorescing dye concentrations of the two mixtures were 20 ppm and 40 ppm. Attenuation coefficient for the five mixtures ranged from 4.8/m to 21.3/m. Variations in volume scattering function with phase angle were typical. Variations in attenuation and absorption coefficient with wavelength were similar for the mixtures without the dye. Attenuation coefficient of the mixtures with the dye increased for wavelengths less than 600 nm due to the dye's strong absorption peak near 500 nm. Reflectance increased as the concentration of Calvert clay increased and peaked near 600 nm. The nonfluorescent dye decreased the magnitude of the peak, but had practically no effect on the variation for wavelengths greater than 640 nm. At wavelengths less than 600 nm, the spectral variations of the mixtures with the dye were significantly different from those mixtures without the dye.

Absorption and emission spectra of Li atoms trapped in rare gas matrices

NASA Astrophysics Data System (ADS)

Wright, J. J.; Balling, L. C.

1980-10-01

Pulsed-dye-laser excitation has been used to investigate the optical absorption and emission spectra of Li atoms trapped in Ar, Kr, and Xe matrices at 10 °K. Attempts to stabilize Li atoms in a Ne matrix at 2 °K were unsuccessful. Results for all three rare gases were qualitatively the same. White light absorption scans showed a single absorption with three peaks centered near the free-atom 2s→2p transition wavelength. The intensity of fluorescence produced by dye-laser excitation within this absorption band was measured as a function of emission wavelength. Excitation of the longest- and shortest-wavelength absorption peaks produced identical emission profiles, but no distinct fluorescence signal was detected when the laser was tuned to the central absorption peaks, indicating that the apparent absorption triplet is actually the superposition of a singlet and a doublet absorption originating from two different trapping sites. No additional absorption bands were detected.

Novel Blue Organic Dye for Dye-Sensitized Solar Cells Achieving High Efficiency in Cobalt-Based Electrolytes and by Co-Sensitization.

PubMed

Hao, Yan; Saygili, Yasemin; Cong, Jiayan; Eriksson, Anna; Yang, Wenxing; Zhang, Jinbao; Polanski, Enrico; Nonomura, Kazuteru; Zakeeruddin, Shaik Mohammed; Grätzel, Michael; Hagfeldt, Anders; Boschloo, Gerrit

2016-12-07

Blue and green dyes as well as NIR-absorbing dyes have attracted great interest because of their excellent ability of absorbing the incident photons in the red and near-infrared range region. A novel blue D-π-A dye (Dyenamo Blue), based on the diketopyrrolopyrrole (DPP)-core, has been designed and synthesized. Assembled with the cobalt bipyridine-based electrolytes, the device with Dyenamo Blue achieved a satisfying efficiency of 7.3% under one sun (AM1.5 G). The co-sensitization strategy was further applied on this blue organic dye together with a red D-π-A dye (D35). The successful co-sensitization outperformed a panchromatic light absorption and improved the photocurrent density; this in addition to the open-circuit potential result in an efficiency of 8.7%. The extended absorption of the sensitization and the slower recombination reaction between the blue dye and TiO 2 surface inhibited by the additional red sensitizer could be the two main reasons for the higher performance. In conclusion, from the results, the highly efficient cobalt-based DSSCs could be achieved with the co-sensitization between red and blue D-π-A organic dyes with a proper design, which showed us the possibility of applying this strategy for future high-performance solar cells.

Fab MOR03268 triggers absorption shift of a diagnostic dye via packaging in a solvent-shielded Fab dimer interface.

PubMed

Hillig, Roman C; Urlinger, Stefanie; Fanghänel, Jörg; Brocks, Bodo; Haenel, Cornelia; Stark, Yvonne; Sülzle, Detlev; Svergun, Dmitri I; Baesler, Siegfried; Malawski, Guido; Moosmayer, Dieter; Menrad, Andreas; Schirner, Michael; Licha, Kai

2008-03-14

Molecular interactions between near-IR fluorescent probes and specific antibodies may be exploited to generate novel smart probes for diagnostic imaging. Using a new phage display technology, we developed such antibody Fab fragments with subnanomolar binding affinity for tetrasulfocyanine, a near-IR in vivo imaging agent. Unexpectedly, some Fabs induced redshifts of the dye absorption peak of up to 44 nm. This is the largest shift reported for a biological system so far. Crystal structure determination and absorption spectroscopy in the crystal in combination with microcalorimetry and small-angle X-ray scattering in solution revealed that the redshift is triggered by formation of a Fab dimer, with tetrasulfocyanine being buried in a fully closed protein cavity within the dimer interface. The derived principle of shifting the absorption peak of a symmetric dye via packaging within a Fab dimer interface may be transferred to other diagnostic fluorophores, opening the way towards smart imaging probes that change their wavelength upon interaction with an antibody.

Visible light water splitting using dye-sensitized oxide semiconductors.

PubMed

Youngblood, W Justin; Lee, Seung-Hyun Anna; Maeda, Kazuhiko; Mallouk, Thomas E

2009-12-21

Researchers are intensively investigating photochemical water splitting as a means of converting solar to chemical energy in the form of fuels. Hydrogen is a key solar fuel because it can be used directly in combustion engines or fuel cells, or combined catalytically with CO(2) to make carbon containing fuels. Different approaches to solar water splitting include semiconductor particles as photocatalysts and photoelectrodes, molecular donor-acceptor systems linked to catalysts for hydrogen and oxygen evolution, and photovoltaic cells coupled directly or indirectly to electrocatalysts. Despite several decades of research, solar hydrogen generation is efficient only in systems that use expensive photovoltaic cells to power water electrolysis. Direct photocatalytic water splitting is a challenging problem because the reaction is thermodynamically uphill. Light absorption results in the formation of energetic charge-separated states in both molecular donor-acceptor systems and semiconductor particles. Unfortunately, energetically favorable charge recombination reactions tend to be much faster than the slow multielectron processes of water oxidation and reduction. Consequently, visible light water splitting has only recently been achieved in semiconductor-based photocatalytic systems and remains an inefficient process. This Account describes our approach to two problems in solar water splitting: the organization of molecules into assemblies that promote long-lived charge separation, and catalysis of the electrolysis reactions, in particular the four-electron oxidation of water. The building blocks of our artificial photosynthetic systems are wide band gap semiconductor particles, photosensitizer and electron relay molecules, and nanoparticle catalysts. We intercalate layered metal oxide semiconductors with metal nanoparticles. These intercalation compounds, when sensitized with [Ru(bpy)(3)](2+) derivatives, catalyze the photoproduction of hydrogen from sacrificial electron donors (EDTA(2-)) or non-sacrificial donors (I(-)). Through exfoliation of layered metal oxide semiconductors, we construct multilayer electron donor-acceptor thin films or sensitized colloids in which individual nanosheets mediate light-driven electron transfer reactions. When sensitizer molecules are "wired" to IrO(2).nH(2)O nanoparticles, a dye-sensitized TiO(2) electrode becomes the photoanode of a water-splitting photoelectrochemical cell. Although this system is an interesting proof-of-concept, the performance of these cells is still poor (approximately 1% quantum yield) and the dye photodegrades rapidly. We can understand the quantum efficiency and degradation in terms of competing kinetic pathways for water oxidation, back electron transfer, and decomposition of the oxidized dye molecules. Laser flash photolysis experiments allow us to measure these competing rates and, in principle, to improve the performance of the cell by changing the architecture of the electron transfer chain.

The chemical bonds effect of anthocyanin and chlorophyll dyes on TiO2 for dye-sensitized solar cell (DSSC)

NASA Astrophysics Data System (ADS)

Ahliha, A. H.; Nurosyid, F.; Supriyanto, A.; Kusumaningsih, T.

2017-11-01

Anthocyanin and chlorophyll dyes have been blended as the photosensitizer of Dye-Sensitized Solar Cell (DSSC). The results study showed the effect of chemical bond dyes on TiO2 and the efficiency of DSSC. Ratio blend of the anthocyanin and chlorophyll dyes are 1:1. The absorbance of dyes and TiO2 were characterized using UV-Vis Spectrophotometer. The chemical bonds contained in TiO2-dyes were characterized using FT-IR spectrophotometer. The efficiency of DSSC was calculated using I-V meter. The absorption spectra of chlorophyll: anthocyanin blend dye solutions and TiO2 films can increase after the dye adsorption. Absorbance characterization of anthocyanin and chlorophyll dye blend solutions showed three peaks at the wavelength of 412 nm; 535.5 nm; and 656.5 nm. Absorbance characterization of spinach before being blend with anthocyanin dyes solutions showed two peaks at the wavelength of 431 nm and 665.5 nm. The absorption spectra of TiO2 films can increase after the dyes adsorption at the wavelength of 400 nm. FT-IR spectra of TiO2 founded the functional groups C-Br, C=C, and O-H. The functional groups founded in anthocyanin: chlorophyll dye blended on the surface of TiO2 are C-Br, C-O, O-H, C-H, C=C, C=O, and O-H. The result showed that the greatest efficiency of 0.0544% at dye red cabbage-spinach. Adsorption blends of anthocyanin and chlorophyll dyes on the surface of TiO2 can be used as the photosensitizer for DSSC.

Multiple electron injection dynamics in linearly-linked two dye co-sensitized nanocrystalline metal oxide electrodes for dye-sensitized solar cells.

PubMed

Shen, Qing; Ogomi, Yuhei; Park, Byung-wook; Inoue, Takafumi; Pandey, Shyam S; Miyamoto, Akari; Fujita, Shinsuke; Katayama, Kenji; Toyoda, Taro; Hayase, Shuzi

2012-04-07

Understanding the electron transfer dynamics at the interface between dye sensitizer and semiconductor nanoparticle is very important for both a fundamental study and development of dye-sensitized solar cells (DSCs), which are a potential candidate for next generation solar cells. In this study, we have characterized the ultrafast photoexcited electron dynamics in a newly produced linearly-linked two dye co-sensitized solar cell using both a transient absorption (TA) and an improved transient grating (TG) technique, in which tin(IV) 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (NcSn) and cis-diisothiocyanato-bis(2,2'-bipyridyl-4,4'-dicarboxylato)ruthenium(II) bis(tetrabutylammonium) (N719) are molecularly and linearly linked and are bonded to the surface of a nanocrystalline tin dioxide (SnO(2)) electrode by a metal-O-metal linkage (i.e. SnO(2)-NcSn-N719). By comparing the TA and TG kinetics of NcSn, N719, and hybrid NcSn-N719 molecules adsorbed onto both of the SnO(2) and zirconium dioxide (ZrO(2)) nanocrystalline films, the forward and backward electron transfer dynamics in SnO(2)-NcSn-N719 were clarified. We found that there are two pathways for electron injection from the linearly-linked two dye molecules (NcSn-N719) to SnO(2). The first is a stepwise electron injection, in which photoexcited electrons first transfer from N719 to NcSn with a transfer time of 0.95 ps and then transfer from NcSn to the conduction band (CB) of SnO(2) with two timescales of 1.6 ps and 4.2 ps. The second is direct photoexcited electron transfer from N719 to the CB of SnO(2) with a timescale of 20-30 ps. On the other hand, back electron transfer from SnO(2) to NcSn is on a timescale of about 2 ns, which is about three orders of magnitude slower compared to the forward electron transfer from NcSn to SnO(2). The back electron transfer from NcSn to N719 is on a timescale of about 40 ps, which is about one order slower compared to the forward electron transfer from N719 to NcSn. These results demonstrate that photoexcited electrons can be effectively injected into SnO(2) from both of the N719 and NcSn dyes.

Coherent Optical Transients and Spectral Line Narrowing Phenomena in Four Wave Mixing Spectroscopies: Theoretical and Experimental Studies.

NASA Astrophysics Data System (ADS)

Dugan, Mark Allen

1990-08-01

The theoretical basis for new signal transients and spectral features generated in field correlated four wave mixing (4WM) spectroscopies is developed. Special attention is given to those signal responses that are sensitive to phase/amplitude correlation among the input driving fields and not simply their intensity correlation. Thus, the cases of incoherent broadband excitation and of coherent short pulsed excitation will be discussed and compared. Applications to the coherent Raman spectroscopies, both electronically nonresonant and fully resonant, are analyzed. Novel interferometric oscillatory behavior is exposed in terms of field-matter detuning beats and matter-matter bi-level and tri-level quantum beats. In addition new detuning resonances are found that have sub-material linewidths and lock onto the mode frequency of the driven chromophore. These spectral features are a member of a class of bichromophore resonant lineshapes arising from nonlinear mixing with correlated driving fields. The origin of such bichromophore resonances can be based on a coupling between two field-matter superposition states driven by correlated fields on separate chromophores. Analytic results are presented and modelled to anticipate the experimental results presented in a following chapter. The onset of resolvable homogeneous electronic memory is reported in room temperature solutions of dye molecules. A narrowing of the homogeneous linewidths with increasing concentration of these dye solutions is observed in sub-picosecond photon echo experiments. This effect is attributed to aggregation which results in a delocalization of the electronic states over several molecules. Ultra -fast spectral diffusion in these dye aggregates is observed in stimulated photon echo measurements. Aggregate bands, seen in the linear absorption spectrum only at high concentrations, can be probed in more dilute solutions with nonlinear four wave mixing.

Spectral study and protein labeling of inclusion complex between dye and calixarene sulfonate.

PubMed

Fei, Xuening; Zhang, Yong; Zhu, Sen; Liu, Lijuan; Yu, Lu

2013-05-01

The host-guest inclusion complex of calix[6]arene sulfonate (SCA6) with thiazole orange (TO) formed in aqueous solution was studied. Absorption and fluorescence techniques were used for the analysis of this inclusion complex. The addition of calixarene sulfonate leads to a decrease in both absorption and fluorescence intensity of the dye, indicating that the inclusion complex was formed. Simultaneously, the inclusion phenomenon of another cyanine dye, Cy3, with calixarene sulfonate was investigated. The stability constant of the two complexes was determined, and the results were compared. The water solubility of TO dye was increased in the presence of calixarene sulfonate, and further protein labeling experiments suggested that this TO-SCA6 complex can act as a fluorescent probe for labeling of biomolecules.

Contribution of the 2(1)Ag state to the third-order optical nonlinearity in a squaraine dye.

PubMed

Andrews, J H; Khaydarov, J D; Singer, K D

1994-07-01

We have measured the third-harmonic response, gamma, of a centrosymmetric squaraine dye (ISQ) in chloroform at a range of frequencies for which the third harmonic is above the strong, narrow peak in the dye's linear absorption spectrum but below the UV absorption band. By fitting the experimental dispersion of gamma using a four-level model, we determine the strength, location, and width of the lowest-lying two-photon transition. We find that the 2(1)Ag state appears just above the 1(1)Bu state in energy and that the 1(1)Bu-2(1)Ag transition moment is somewhat smaller than the transition moment between the ground state and the 1(1)Bu state but much larger than previously predicted for comparable squaraine dyes.

Three-photon absorption process in organic dyes enhanced by surface plasmon resonance

NASA Astrophysics Data System (ADS)

Cohanoschi, Ion

2006-07-01

Multi-photon absorption processes have received significant attention from the scientific community during the last decade, mainly because of their potential applications in optical limiting, data storage and biomedical fields. Perhaps, one of the most investigated processes studied so far has been two-photon absorption (2PA). These investigations have resulted in successful applications in all the fields mentioned above. However, 2PA present some limitations in the biomedical field when pumping at typical 2PA wavelengths. In order to overcome these limitations, three-photon absorption (3PA) process has been proposed. However, 3PA in organic molecules has a disadvantage, typical values of sigma3' are small (10-81 cm6s 2/photon2), therefore, 3PA excitation requires high irradiances to induce the promotion of electrons from the ground state to the final excited state. To overcome this obstacle, specific molecules that exhibit large 3PA cross-section must be designed. Thus far, there is a lack of systematic studies that correlate 3PA processes with the molecular structure of organic compounds. In order to fill the existent gap in 3PA molecular engineering, in this dissertation we have investigated the structure/property relationship for a new family of fluorene derivatives with very high three-photon absorption cross-sections. We demonstrated that the symmetric intramolecular charge transfer as well as the pi-electron conjugation length enhances the 3PA cross-section of fluorene derivatives. In addition, we showed that the withdrawing electron character of the attractor groups in a pull-pull geometry proved greater 3PA cross-section. After looking for alternative ways to enhance the effective sigma 3' of organic molecules, we investigated the enhancement of two- and three-photon absorption processes by means of Surface Plasmon. We demonstrated an enhancement of the effective two- and three-photon absorption cross-section of an organic compound of 480 and 30 folds, respectively. We proved that the enhancement is a direct consequence of the electric field enhancement at a metal/buffer interface. Next, motivated by the demands for new materials with enhanced nonlinear optical properties, we studied the 3PA of Hematoporphyrin IX and J-aggregate supramolecular systems. As a result, we were able to propose the use of 3PA in photodynamic therapy using Photofrin, the only drug approved by the FDA for PDT.

Direct local solvent probing by transient infrared spectroscopy reveals the mechanism of hydrogen-bond induced nonradiative deactivation† †Electronic supplementary information (ESI) available: Experimental details, basic photophysics of ADA, transient electronic absorption, additional steady-state and transient IR spectra. See DOI: 10.1039/c7sc00437k Click here for additional data file.

PubMed Central

Dereka, Bogdan

2017-01-01

The fluorescence quenching of organic dyes via H-bonding interactions is a well-known phenomenon. However, the mechanism of this Hydrogen-Bond Induced Nonradiative Deactivation (HBIND) is not understood. Insight into this process is obtained by probing in the infrared the O–H stretching vibration of the solvent after electronic excitation of a dye with H-bond accepting cyano groups. The fluorescence lifetime of this dye was previously found to decrease from 1.5 ns to 110 ps when going from an aprotic solvent to the strongly protic hexafluoroisopropanol (HFP). Prompt strengthening of the H-bond with the dye was identified by the presence of a broad positive O–H band of HFP, located at lower frequency than the O–H band of the pure solvent. Further strengthening occurs within a few picoseconds before the excited H-bonded complex decays to the ground state in 110 ps. The latter process is accompanied by the dissipation of energy from the dye to the solvent and the rise of a characteristic hot solvent band in the transient spectrum. Polarization-resolved measurements evidence a collinear alignment of the nitrile and hydroxyl groups in the H-bonded complex, which persists during the whole excited-state lifetime. Measurements in other fluorinated alcohols and in chloroform/HFP mixtures reveal that the HBIND efficiency depends not only on the strength of the H-bond interactions between the dye and the solvent but also on the ability of the solvent to form an extended H-bond network. The HBIND process can be viewed as an enhanced internal conversion of an excited complex consisting of the dye molecule connected to a large H-bond network. PMID:28970892

Near-infrared indocyanine dye permits real-time characterization of both venous and lymphatic circulation

NASA Astrophysics Data System (ADS)

Kurahashi, Toshikazu; Iwatsuki, Katsuyuki; Onishi, Tetsuro; Arai, Tetsuya; Teranishi, Katsunori; Hirata, Hitoshi

2016-08-01

We investigated the optical properties of a near-infrared (NIR) fluorochrome, di-β-cyclodextrin-binding indocyanine derivative (TK-1), and its pharmacokinetic differences with indocyanine green (ICG). TK-1 was designed to have hydrophilic cyclodextrin molecules and, thus, for higher water solubility and smaller particle sizes than the plasma protein-bound ICG. We compared optical properties such as the absorption and fluorescence spectra, quantum yield, and photostability between both dyes in vitro. In addition, we subcutaneously injected a 1 mM solution of TK-1 or ICG into the hind footpad of rats and observed real-time NIR fluorescence intensities in their femoral veins and accompanying lymphatics at the exposed groin site to analyze the dye pharmacokinetics. These optical experiments demonstrated that TK-1 has high water solubility, a low self-aggregation tendency, and high optical and chemical stabilities. Our in vivo imaging showed that TK-1 was transported via peripheral venous flow and lymphatic flow, whereas ICG was drained only through lymphatics. The results of this study showed that lymphatic and venous transport can be differentially regulated and is most likely influenced primarily by particle size, and that TK-1 can enable real-time NIR fluorescence imaging of whole fluids and solute movement via both microvessels and lymphatics, which conventional ICG cannot achieve.

Preparation of Platinum (Pt) Counter Electrode Coated by Electrochemical Technique at High Temperature for Dye-sensitized Solar Cell (DSSC) Application

NASA Astrophysics Data System (ADS)

Ponken, Tanachai; Tagsin, Kamonlapron; Suwannakhun, Chuleerat; Luecha, Jakkrit; Choawunklang, Wijit

2017-09-01

Pt counter electrode was coated by electrochemical method. Electrolyte solution was synthesized by platinum (IV) choloride (PtCl4) powder dissolved in hydrochloric acid solution. Pt films were deposited on the FTO substrate. Deposition time of 10, 30 and 60 minutes, the coating current of 5, 10, 15 and 20 mA and electrolyte solution temperatures for Pt layer synthesis of 25, 30 and 40°C were varied. Surface morphology and optical properties was analyzed by digital microscopic and UV-vis spectrophotometer. Pt films exhibit uniform surface area highly for all the conditions of coating current in the deposition time of 30 and 40 minutes at 40°C. Transmittance values of Pt films deposited on FTO substrate has approximately of 5 to 50 % show that occur high reflection corresponding to dye molecule absorption increases. DSSC device was fabricated from the TiO2 standard and immersed in dye N719 for 24 hours. Efficiency was measured by solar simulator. Efficiency value obtains as high as 5.91 % for the coating current, deposition time and solution temperature of 15 mA, 30 minutes and 40°C. Summary, influence of temperature effects efficiency increasing. Pt counter electrode can be prepared easily and the suitable usefully for DSSC.

Sorption equilibrium, thermodynamics and pH-indicator properties of cresyl violet dye/bentonite composite system.

PubMed

Georgieva, Nedyalka; Yaneva, Zvezdelina; Dermendzhieva, Diyana

2017-09-01

The aim of the present study was to develop cresyl violet (CV)/bentonite composite system, to investigate the equilibrium sorption of the fluorescent dye on bentonite, to determine the characteristic equilibrium and thermodynamic parameters of the system by appropriate empirical isotherm models and to assess its pH-indicator properties. The absorption characteristics of CV solutions were investigated by UV/VIS spectrophotometer. Equilibrium experiments were conducted and the experimental data were modelled by six mathematical isotherm models. The analyses of the experimental data showed that bentonite exhibited significantly high capacity - 169.92 mg/g, towards CV. The encapsulation efficiency was 85%. The Langmuir, Flory-Huggins and El-Awady models best represented the experimental results. The free Gibbs energy of adsorption (ΔG o ) was calculated on the basis of the values of the equilibrium coefficients determined by the proposed models. The values of ΔG determined by the Langmuir, Temkin and Flory-Huggins models are within the range -20 to -40 kJ/mol, which indicates that the adsorption process is spontaneous and chemisorption takes place due to charge sharing or transfer from the dye molecules to the sorbent surface as a coordinate type of bond. The investigations of the obtained CV/bentonite hybrid systems for application as pH-markers showed satisfactory results.

Multifunctional Fe3O4@SiO2-Au Satellite Structured SERS Probe for Charge Selective Detection of Food Dyes.

PubMed

Sun, Zhenli; Du, Jingjing; Yan, Li; Chen, Shu; Yang, Zhilin; Jing, Chuanyong

2016-02-10

Nanofabrication of multifunctional surface-enhanced Raman scattering (SERS) substrates is strongly desirable but currently remains a challenge. The motivation of this study was to design such a substrate, a versatile core-satellite Fe3O4@SiO2-Au (FA) hetero-nanostructure, and demonstrate its use for charge-selective detection of food dye molecules as an exemplary application. Our experimental results and three-dimensional finite difference time domain (FDTD) simulation suggest that tuning the Au nanoparticle (NP) gap to sub-10 nm, which could be readily accomplished, substantially enhanced the Raman signals. Further layer-by-layer deposition of a charged polyelectrolyte on this magnetic SERS substrate induced active adsorption and selective detection of food dye molecules of opposite charge on the substrates. Molecular dynamics (MD) simulations suggest that the selective SERS enhancement could be attributed to the high affinity and close contact (within a 20 Å range) between the substrate and molecules. Density function theory (DFT) calculations confirm the charge transfer from food dye molecules to Au NPs via the polyelectrolytes. This multifunctional SERS platform provides easy separation and selective detection of charged molecules from complex chemical mixtures.

Design of two-photon molecular tandem architectures for solar cells by ab initio theory

DOE PAGES

Ornso, Kristian B.; Garcia-Lastra, Juan M.; De La Torre, Gema; ...

2015-03-04

An extensive database of spectroscopic properties of molecules from ab initio calculations is used to design molecular complexes for use in tandem solar cells that convert two photons into a single electron–hole pair, thereby increasing the output voltage while covering a wider spectral range. Three different architectures are considered: the first two involve a complex consisting of two dye molecules with appropriately matched frontier orbitals, connected by a molecular diode. Optimized combinations of dye molecules are determined by taking advantage of our computational database of the structural and energetic properties of several thousand porphyrin dyes. The third design is amore » molecular analogy of the intermediate band solar cell, and involves a single dye molecule with strong intersystem crossing to ensure a long lifetime of the intermediate state. Based on the calculated energy levels and molecular orbitals, energy diagrams are presented for the individual steps in the operation of such tandem solar cells. We find that theoretical open circuit voltages of up to 1.8 V can be achieved using these tandem designs. Questions about the practical implementation of prototypical devices, such as the synthesis of the tandem molecules and potential loss mechanisms, are addressed.« less

Curcumin-sensitized TiO2 for enhanced photodegradation of dyes under visible light

NASA Astrophysics Data System (ADS)

Buddee, Supat; Wongnawa, Sumpun; Sriprang, Pimpaporn; Sriwong, Chaval

2014-04-01

Curcumin was coated on P25 TiO2 by using impregnation method from freshly prepared curcumin solution. The resulting products (Cur-TiO2-P25) was studied by several techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier-transformed infrared spectroscopy, specific surface area by the Brunauer-Emmett-Teller method, and UV-Vis diffused reflectance spectroscopy. Experimental results revealed that impregnation of curcumin at 0.5, 3, 5, and 7 wt% did not affect the native phase of anatase and rutile in P25 significantly, however, it caused red shift of absorption onset in all curcumin-coated samples. The Cur-TiO2-P25 showed enhanced adsorption efficiency and increased photocatalytic activity under visible light with optimal result at 5 wt% curcumin content. Commercial anatase and rutile coated with curcumin (Cur-TiO2-an and Cur-TiO2-ru) were also prepared by the same method for the use in comparative studies of photodegradation of dyes. Cur-TiO2-an and Cur-TiO2-ru were also characterized with some selected equipment above but not as extensively as the Cur-TiO2-P25. Curcumin coating helped improve photocatalytic efficiencies of P25 and anatase but not for rutile. The mechanism of photocatalytic reaction was proposed that under visible light irradiation, curcumin molecule could act as dye sensitizing agent that injected electron into the conduction band of TiO2 leading to photodegradation of dyes.

Theory of liquid crystal orientation under action of light wave field and aligning surfaces

NASA Astrophysics Data System (ADS)

Dadivanyan, A. K.; Chausov, D. N.; Belyaev, V. V.; Barabanova, N. N.; Chausova, O. V.; Kuleshova, Yu D.

2018-03-01

Theoretical models developed in the MRSU group under leadership of Professor Artem Dadivanyan in area of the LC orientation and photo-induced effects are presented. Angular distribution functions of the dye and liquid crystal molecules under action of intensive light beam have been derived. The number of molecules in cluster is estimated. A model of dimers formation in the photoalignment dye is suggested that explains influence of the dye molecular structure on both polar and azimuthal anchoring energy.

Green synthesis, structure and fluorescence spectra of new azacyanine dyes

NASA Astrophysics Data System (ADS)

Enchev, Venelin; Gadjev, Nikolai; Angelov, Ivan; Minkovska, Stela; Kurutos, Atanas; Markova, Nadezhda; Deligeorgiev, Todor

2017-11-01

A series of symmetric and unsymmetric monomethine azacyanine dyes (monomethine azacyanine and merocyanine sulfobetaines) were synthesized with moderate to high yields via a novel method using microwave irradiation. The compounds are derived from a condensation reaction between 2-thiomethylbenzotiazolium salts and 2-imino-3-methylbenzothiazolines proceeded under microwave irradiation. The synthetic approach involves the use of green solvent and absence of basic reagent. TD-DFT calculations were performed to simulate absorption and fluorescent spectra of synthesized dyes. Absorption maxima, λmax, of the studied dyes were found in the range 364-394 nm. Molar absorbtivities were evaluated in between 40300 and 59200 mol-1 dm3 cm-1. Fluorescence maxima, λfl, were registered around 418-448 nm upon excitation at 350 nm. A slight displacements of theoretically estimated absorption maxima according to experimental ones is observed. The differences are most probably due to the fact that the DFT calculations were carried out without taking into account the solvent effect. In addition, the merocyanine sulfobetaines also fluorescence in blue optical range (420-480 nm) at excitation in red range (630-650 nm).

DFT, FT-IR, FT-Raman and NMR studies of 4-(substituted phenylazo)-3,5-diacetamido-1H-pyrazoles

NASA Astrophysics Data System (ADS)

Kınalı, Selin; Demirci, Serkan; Çalışır, Zühre; Kurt, Mustafa; Ataç, Ahmet

2011-05-01

We present a detailed analysis of the structural and vibrational spectra of some novel azo dyes. 2-(Substituted phenylazo)malononitriles were synthesized by the coupling reaction of the diazonium salts, which were prepared with the use of various aniline derivatives with malononitrile, and then 4-(substituted phenylazo)-3,5-diamino-1H-pyrazole azo dyes were obtained via the ring closure of the azo compounds with hydrazine monohydrate. The experimental and theoretical vibrational spectra of azo dyes were studied. The structural and spectroscopic analysis of the molecules were carried out by using Becke's three-parameters hybrid functional (B3LYP) and density functional harmonic calculations. The 1H nuclear magnetic resonance (NMR) chemical shifts of the azo dye molecules were calculated using the gauge-invariant-atomic orbital (GIAO) method. The calculated vibrational wavenumbers and chemical shifts were compared with the experimental data of the molecules.

Inclusion of aggregation effect to evaluate the performance of organic dyes in dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Sun, Kenan; Zhang, Weiyi; Heng, Panpan; Wang, Li; Zhang, Jinglai

2018-05-01

Two new indoline-based D-A-π-A dyes, D3F and D3F2 (see Scheme 1), are developed on the basis of the reported D3 by insertion of one or two F atoms on benzothiadiazole group. Our central aim is to explore high-efficiency organic dyes applied in dye-sensitized solar cells by inclusion of a simple group rather than by employment of new complicated groups. The performance of two new designed organic dyes, D3F and D3F2, is compared with that of D3 from various aspects including absorption spectrum, light harvesting efficiency, driving force, and open-circuit voltage. Besides the isolated dye, the interfacial property between dye and TiO2 surface is studied. D3F and D3F2 do not show absolute superiority than D3 not only for the isolated dyes but also for the monomeric adsorption system. However, D3F and D3F2 would effectively reduce the influence of aggregation resulting in the much smaller intermolecular electronic coupling. Although the aggregation has attracted much attention recently, it is studied alone in most of studies. To comprehensively evaluate the performance of dye-sensitized solar cells, it is necessary to consider aggregation along with electron injection time from dye into TiO2 rather than only static items, such as, band gap and absorption region.

Thermally stable molecules with large dipole moments and polarizabilities and applications thereof

NASA Technical Reports Server (NTRS)

Marder, Seth R. (Inventor); Peyghambarian, Nasser (Inventor); Kippelen, Bernard (Inventor); Volodin, Boris (Inventor); Hendrickx, Eric (Inventor)

2002-01-01

Disclosed are fused ring bridge, ring-locked dyes that form thermally stable photorefractive compositions. The fused ring bridge structures are .pi.-conjugated bonds in benzene-, naphthalene- or anthracene-derived fused ring systems that connect donor and acceptor groups. The donor and acceptor groups contribute to a high molecular dipole moment and linear polarizability anisotropy. The polarization characteristics of the dye molecules are stabilized since the bonds in the fused ring bridge are not susceptible to rotation, reducing the opportunity for photoisomerization. The dyes are compatible with polymeric compositions, including thermoplastics. The dyes are electrically neutral but have charge transport, electronic and orientational properties such that upon illumination of a composition containing the dye, the dye facilitates refractive index modulation and a photorefractive effect that can be utilized advantageously in numerous applications such as in optical quality devices and biological imaging.

Adsorption of the diazo dye Direct Red 23 onto a zinc oxide surface: A spectroscopic study

NASA Astrophysics Data System (ADS)

Lucilha, Adriana Campano; Bonancêa, Carlos Eduardo; Barreto, Wagner José; Takashima, Keiko

2010-01-01

The adsorption of the diazo dye Direct Red 23 onto a zinc oxide surface at 30 °C in the dark was investigated. The color reduction was monitored by spectrophotometry at 503 nm. The FTIR and Raman spectra of the Direct Red 23 adsorption as a function of ZnO concentration were registered. From the PM3 semi-empirical calculations of the atomic charge density and dipole moment of the Direct Red 23 molecule, it was demonstrated that the azo dye molecule may be adsorbed onto the ZnO surface through molecule geometry modifications, enhancing the interfacial area causing a variation in the bonding frequencies.

Photoinduced energy and electron transfer processes in hexapyropheophorbide a- fullerene [C(60)] molecular systems.

PubMed

Regehly, Martin; Ermilov, Eugeny A; Helmreich, Matthias; Hirsch, Andreas; Jux, Norbert; Röder, Beate

2007-02-08

The photophysical properties of the novel hexapyropheophorbide a (P6), and hexakis (pyropheophorbide a)-C60 (FP6) were studied and compared with those of hexakis (pyropheophorbide a)-fullerene [5:1] hexaadduct (FHP6). It was found that after light absorption the pyropheophorbide a molecules in all three compounds undergo very efficient energy transfer as well as partly excitonic interactions. The last process results in the formation of energy traps, which could be resolved experimentally. For P6, due to shorter distances between neighboring dye molecules, stronger interactions between pyropheophorbide a units than for FHP6 were observed. As a consequence, the excitation energy is delivered rapidly to traps formed by stacked pyropheophorbide a molecules resulting in the reduction of fluorescence, intersystem crossing, and singlet oxygen quantum yields compared to the values of FHP6. For FP6 the reduction of these values is much stronger due to an additional fast and efficient deactivation process, namely photoinduced electron transfer from pyropheophorbide a to the fullerene moiety. Consequently, FP6 can be considered as a combination of a light-harvesting system consisting of several separate pyropheophorbide a molecules and a charge-separating center.

Cyanine dyes as optical contrast agents for ophthalmological surgery.

PubMed

Langhals, Heinz; Varja, Ana; Laubichler, Peter; Kernt, Marcus; Eibl, Kirsten; Haritoglou, Christos

2011-06-09

Cyanine dyes were prepared as optical contrast media for supporting the surgery of the lamina limitans interna (LLI) of the retina and other structures of the human eye. Their absorption spectra were adapted both to the spectral sensitivity of the human eye and to standard illumination. The contrast could be further amplified by the application of the strong fluorescence of the dyes used. The binding of the dyes to various surfaces was studied. No toxic effects could be detected for the applied dyes.

Indigo Dye Derived from Indigofera Tinctoria as Natural Food Colorant

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Ramelan, A. H.; Wardani, D. K.; Aini, F. N.; Sari, P. L.; Tamtama, B. P. N.; Kristiawan, Y. R.

2017-04-01

Recently, the uses of dyes are increasingly widespread especially in foods and beverages as food colors to attract the consumers. The dye that currently attracts is indigo. Indigo is a group of carbonyl compounds, one of the oldest known dyes in terms of natural blue dye derived from the Indigofera tinctoria plant. The use of indigo as a natural food dye intended to reduce the use of synthetic dyes are carcinogenic impact. The method used in this study includes the analysis of indigo using UV-Vis spectrophotometry and FTIR analysis. Based on the UV-Vis Spectrophotometer analysis results with the various concentrations of 0.002 mg/mL; 0.004 mg/mL; 0.006 mg/mL and 0.008 mg/mL were obtained maximum absorption peak at wavelength of 550-700 nm. The indigo dyes in various concentrations produce a stable pH at an average pH 9, therefore it can make the colors not easily fade (strong staining). Based on infrared spectrophotometer measurement were obtained absorption spectrum at 3100-3500 cm-1 as primary N-H and secondary amine, 1600 cm-1 as aromatic C=C, 1000-1350 cm-1 as aromatic C-N, 690-900 cm-1 as aromatic C-H.

Photoacoustic spectroscopic studies of polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Zaidi, Zahid H.; Kumar, Pardeep; Garg, R. K.

1999-02-01

Because of their involvement in environmental pollutants, in carcinogenic activity, plastics, pharmaceuticals, synthesis of some laser dyes and presence in interstellar space etc., Polycyclic aromatic hydrocarbons (PAHs) are important. As their structure and properties can be varied systematically, they form a beautiful class of molecules for experimental and quantum chemical investigations. These molecules are being studied for last several years by using conventional spectroscopy. In recent years, Photoacoustic (PA) spectroscopy has emerged as a new non-destructive technique with unique capability and sensitivity. The PA effect is the process of generation of acoustic waves in a sample resulting from the absorption of photons. This technique not only reveals non- radiative transitions but also provides information about forbidden singlet-triplet transitions which are not observed normally by the conventional spectroscopy. The present paper deals with the spectroscopic studies of some PAH molecules by PA spectroscopy in the region 250 - 400 nm. The CNDO/S-CI method is used to calculate the electronic transitions with the optimized geometries. A good agreement is found between the experimental and calculated results.

Self-assembled near-infrared dye nanoparticles as a selective protein sensor by activation of a dormant fluorophore.

PubMed

Anees, Palapuravan; Sreejith, Sivaramapanicker; Ajayaghosh, Ayyappanpillai

2014-09-24

Design of selective sensors for a specific analyte in blood serum, which contains a large number of proteins, small molecules, and ions, is important in clinical diagnostics. While metal and polymeric nanoparticle conjugates have been used as sensors, small molecular assemblies have rarely been exploited for the selective sensing of a protein in blood serum. Herein we demonstrate how a nonspecific small molecular fluorescent dye can be empowered to form a selective protein sensor as illustrated with a thiol-sensitive near-IR squaraine (Sq) dye (λabs= 670 nm, λem= 700 nm). The dye self-assembles to form nonfluorescent nanoparticles (Dh = 200 nm) which selectively respond to human serum albumin (HSA) in the presence of other thiol-containing molecules and proteins by triggering a green fluorescence. This selective response of the dye nanoparticles allowed detection and quantification of HSA in blood serum with a sensitivity limit of 3 nM. Notably, the Sq dye in solution state is nonselective and responds to any thiol-containing proteins and small molecules. The sensing mechanism involves HSA specific controlled disassembly of the Sq nanoparticles to the molecular dye by a noncovalent binding process and its subsequent reaction with the thiol moiety of the protein, triggering the green emission of a dormant fluorophore present in the dye. This study demonstrates the power of a self-assembled small molecular fluorophore for protein sensing and is a simple chemical tool for the clinical diagnosis of blood serum.

ANALYSIS OF ANIONIC METALLIZED AZO AND FORMAZAN DYES BY CAPILLARY ELECTROPHORESIS/MASS SPECTROMETRY

EPA Science Inventory

Capillary electrophoresis-mass spectrometry was applied to the separation of several anionic dyes containing copper(II), chromium(III), or cobalt(III) as part of the dye molecule. The dyes were separated using a 110 cmX50 mu m uncoated fused-silica capillary and a 5 mM ammonium a...

Impact of natural photosensitizer extraction solvent upon light absorbance in dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Suhaimi, Suriati; Mohamed Siddick, Siti Zubaidah; Ahmad Hambali, Nor Azura Malini; Retnasamy, Vithyacharan; Abdul Wahid, Mohamad Halim; Mohamad Shahimin, Mukhzeer

2017-02-01

Natural pigmentations of Ardisia, Bawang Sabrang, Harum Manis mango, Oxalis Triangularis and Rosella were used to study the general trend in performance of dyes as a photosensitizer in the application of dye-sensitized solar cells (DSSCs) based on optical light absorbance and photoelectrochemical characteristics. From the Ultraviolet-Visible Spectrophotometer with the recorded absorption measurements in the range between 400 nm to 800 nm, the dyes extracted from Rosella and Oxalis Triangularis in water solvent exhibited the conversion efficiency up to 0.68% and 0.67%, respectively. The light absorbance peak for dye extracted from Ardisia, Bawang Sabrang, Oxalis Triangularis and Rosella in water and ethanol solvent resulted in the range between 500 nm to 650 nm, while the Harum Manis mango resulted in the broader spectra in both water and ethanol solvent. The light absorbance spectra of each the dyes shows shifted wavelength spectrum when the extracted dye is adsorbed onto TiO2 film surface that might influenced the absorption of light by TiO2 particle in the visible region. The capabilities of the dyes to absorb light when bonded onto the TiO2 photoanode was found to be significant with the current-voltage conversion of the cell. The results demonstrates just the tip of the vastness of natural dyes' (native to tropical region) feasibility and applicability as a photosensitizer.

Rational Molecular Engineering of Indoline-Based D-A-π-A Organic Sensitizers for Long-Wavelength-Responsive Dye-Sensitized Solar Cells.

PubMed

Zhang, Weiwei; Wu, Yongzhen; Zhu, Haibo; Chai, Qipeng; Liu, Jingchuan; Li, Hui; Song, Xiongrong; Zhu, Wei-Hong

2015-12-09

Indoline-based D-A-π-A organic sensitizers are promising candidates for highly efficient and long-term stable dye-sensitized solar cells (DSSCs). In order to further broaden the spectral response of the known indoline dye WS-2, we rationally engineer the molecular structure through enhancing the electron donor and extending the π-bridge, resulting in two novel indoline-based D-A-π-A organic sensitizers WS-92 and WS-95. By replacing the 4-methylphenyl group on the indoline donor of WS-2 with a more electron-rich carbazole unit, the intramolecular charge transfer (ICT) absorption band of dye WS-92 is slightly red-shifted from 550 nm (WS-2) to 554 nm (WS-92). In comparison, the incorporation of a larger π-bridge of cyclopentadithiophene (CPDT) unit in dye WS-95 not only greatly bathochromatically tunes the absorption band to 574 nm but also largely enhances the molar extinction coefficients (ε), thus dramatically improving the light-harvesting capability. Under the standard global AM 1.5 solar light condition, the photovoltaic performances of both organic dyes have been evaluated in DSSCs on the basis of the iodide/triiodide electrolyte without any coadsorbent or cosensitizer. The DSSCs based on WS-95 display better device performance with power conversion efficiency (η) of 7.69%. The additional coadsorbent in the dye bath of WS-95 does not improve the photovoltaic performance, indicative of its negligible dye aggregation, which can be rationalized by the grafted dioctyl chains on the CPDT unit. The cosensitization of WS-95 with a short absorption wavelength dye S2 enhances the IPCE and improves the η to 9.18%. Our results indicate that extending the π-spacer is more rational than enhancing the electron donor in terms of broadening the spectral response of indoline-based D-A-π-A organic sensitizers.

Removal of Acid Orange 7 dye from aqueous solutions by adsorption onto Kenya tea pulps; granulated shape

PubMed Central

Naraghi, Behnaz; Zabihi, Fahimeh; Narooie, Mohammad Reza; Saeidi, Mahdi; Biglari, Hamed

2017-01-01

Background and Aim Water resources pollution control is one of the main challenges of our time for researchers. Colored wastewater discharges caused by textile industry activities has added to the concern. In this study, removal of Acid Orange 7 dye (AO7) using Kenya Tea residue absorbent (granular) has been studied. Methods This cross-sectional study was conducted in 2016. In this work, initially, tea residue was prepared in three forms of raw, treated with concentrated phosphoric acid, and carbonated, at temperatures of 350, 450 and 500 °C in the chemistry laboratory of Gonabad University of Medical Sciences. Then, efficiency of the above absorbents in the removal of Acid Orange 7 dye in initial concentrations of dye as 50–500 mg/l from water samples in terms of pH 2–10 and 1–10 g/l of adsorbent dose within 20 to 300 minutes was investigated. In addition, their subordination from Langmuir and Freundlich absorption isotherms was also determined. Concentration changes in Acid Orange 7 dye at a wavelength of 483 nm was determined by spectrophotometry and results were reported using descriptive statistics. Results Results showed that efficiency of Acid Orange 7 dye removal is higher in acidic pH and higher adsorbent dosage. The highest efficiency of Acid Orange 7 dye removal was 98.41% by raw tea residue absorbent at pH 2, reaction time was 120 minutes and initial concentration of dye was 50 mg/l, which was obtained at adsorbent dosage of 10 g/l. It was determined that the mechanism of absorption acceptably follows Freundlich absorption isotherm (R2=0.97). Conclusion Due to the availability and very low price, optimal performance of Kenya tea raw residue (granular) in Acid Orange 7 dye removal, it can be used as an efficient surface absorber in an absorber from colored wastewater. PMID:28713501

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.

Supramolecular order following binding of the dichroic birefringent sulfonic dye Ponceau SS to collagen fibers.

PubMed

Vidal, B C; Mello, M L S

2005-06-15

The optical anisotropies (linear dichroism or LD and birefringence) of crystalline aggregates of the sulfonic azo-dye Ponceau SS and of dye complexed with chicken tendon collagen fibers were investigated in order to assess their polarizing properties and similarity to liquid crystals. In some experiments, the staining was preceded by treatment with picric acid. Crystalline fibrous aggregates of the dye had a negative LD, and their electronic transitions were oriented perpendicular to the filamentary structures. The binding of Ponceau SS molecules to the collagen fibers altered the LD signal, with variations in the fiber orientation affecting the resulting dichroic ratios. The long axis of the rod-like dye molecule was assumed to be bound in register, parallel to the collagen fiber. Picric acid did not affect the oriented binding of the azo dye to collagen fibers. There were differences in the optical anisotropy of Ponceau SS-stained tendons from 21-day-old and 41-day-old chickens, indicating that Ponceau SS was able to distinguish between different ordered states of macromolecular aggregation in chicken tendon collagen fibers. In the presence of dichroic rod-like azo-dye molecules such as Ponceau SS, collagen also formed structures with a much higher degree of orientation. The presence of LD in the Ponceau SS-collagen complex even in unpolarized light indicated that this complex can act as a polarizer. Copyright 2005 Wiley Periodicals, Inc.

Exploring the dynamics of fluorescence staining of bacteria with cyanine dyes for the development of kinetic assays

NASA Astrophysics Data System (ADS)

Thomas, Marlon Sheldon

Bacterial infections continue to be one of the major health risks in the United States. The common occurrence of such infection is one of the major contributors to the high cost of health care and significant patient mortality. The work presented in this thesis describes spectroscopic studies that will contribute to the development of a fluorescent assay that may allow the rapid identification of bacterial species. Herein, the optical interactions between six bacterial species and a series of thiacyanine dyes are investigated. The interactions between the dyes and the bacterial species are hypothesized to be species-specific. For this thesis, two Gram-negative strains, Escherichia coli (E. coli) TOP10 and Enterobacter aerogenes; two Gram-positive bacterial strains, Bacillus sphaericus and Bacillus subtilis; and two Bacillus endospores, B. globigii and B. thuringiensis, were used to test the proposed hypothesis. A series of three thiacyanine dyes---3,3'-diethylthiacyanine iodide (THIA), 3,3'-diethylthiacarbocyanine iodide (THC) and thiazole orange (THO)---were used as fluorescent probes. The basis of our spectroscopic study was to explore the bacterium-induced interactions of the bacterial cells with the individual thiacyanine dyes or with a mixture of the three dyes. Steady-state absorption spectroscopy revealed that the different bacterial species altered the absorption properties of the dyes. Mixed-dye solutions gave unique absorption patterns for each bacteria tested, with competitive binding observed between the bacteria and spectrophotometric probes (thiacyanine dyes). Emission spectroscopy recorded changes in the emission spectra of THIA following the introduction of bacterial cells. Experimental results revealed that the emission enhancement of the dyes resulted from increases in the emission quantum yield of the thiacyanine dyes upon binding to the bacteria cellular components. The recorded emission enhancement data were fitted to an exponential (mono-exponential or bi-exponential) function, and time constants were extracted by regressing on the experimental data. The addition of the TWEEN surfactants decreased the rate at which the dyes interacted with the bacterial cells, which typically resulted in larger time constants derived from an exponential fit. ANOVA analysis of the time constants confirmed that the values of the time constants clustered in a narrow range and were independent of dye concentration and weakly dependent on cell density.

High ink absorption performance of inkjet printing based on SiO2@Al13 core-shell composites

NASA Astrophysics Data System (ADS)

Chen, YiFan; Jiang, Bo; Liu, Li; Du, Yunzhe; Zhang, Tong; Zhao, LiWei; Huang, YuDong

2018-04-01

The increasing growth of the inkjet market makes the inkjet printing more necessary. A composite material based on core-shell structure has been developed and applied to prepare inkjet printing layer. In this contribution, the ink printing record layers based on SiO2@Al13 core-shell composite was elaborated. The prepared core-shell composite materials were characterized by X-ray photoelectron spectroscopy (XPS), zeta potential, X-ray diffraction (XRD), scanning electron microscopy (SEM). The results proved the presence of electrostatic adsorption between SiO2 molecules and Al13 molecules with the formation of the well-dispersed system. In addition, based on the adsorption and the liquid permeability analysis, SiO2@Al13 ink printing record layer achieved a relatively high ink uptake (2.5 gmm-1) and permeability (87%), respectively. The smoothness and glossiness of SiO2@Al13 record layers were higher than SiO2 record layers. The core-shell structure facilitated the dispersion of the silica, thereby improved its ink absorption performance and made the clear printed image. Thus, the proposed procedure based on SiO2@Al13 core-shell structure of dye particles could be applied as a promising strategy for inkjet printing.

Adsorption and Corrosion Inhibition Studies of Some Selected Dyes as Corrosion Inhibitors for Mild Steel in Acidic Medium: Gravimetric, Electrochemical, Quantum Chemical Studies and Synergistic Effect with Iodide Ions.

PubMed

Peme, Thabo; Olasunkanmi, Lukman O; Bahadur, Indra; Adekunle, Abolanle S; Kabanda, Mwadham M; Ebenso, Eno E

2015-09-02

The corrosion inhibition properties of some organic dyes, namely Sunset Yellow (SS), Amaranth (AM), Allura Red (AR), Tartrazine (TZ) and Fast Green (FG), for mild steel corrosion in 0.5 M HCl solution, were investigated using gravimetric, potentiodynamic polarization techniques and quantum chemical calculations. The results showed that the studied dyes are good corrosion inhibitors with enhanced inhibition efficiencies. The inhibition efficiency of all the studied dyes increases with increase in concentration, and decreases with increase in temperature. The results showed that the inhibition efficiency of the dyes increases in the presence of KI due to synergistic interactions of the dye molecules with iodide (I(-)) ions. Potentiodynamic polarization results revealed that the studied dyes are mixed-type inhibitors both in the absence and presence of KI. The adsorption of the studied dyes on mild steel surface, with and without KI, obeys the Langmuir adsorption isotherm and involves physical adsorption mechanism. Quantum chemical calculations revealed that the most likely sites in the dye molecules for interactions with mild steel are the S, O, and N heteroatoms.

Effect of composition of chlorophyll and ruthenium dyes mixture (hybrid) on the dye-sensitized solar cell performance

NASA Astrophysics Data System (ADS)

Pratiwi, D. D.; Nurosyid, F.; Kusumandari; Supriyanto, A.; Suryana, R.

2018-03-01

The fabrication of dye-sensitized solar cell (DSSC) has been conducted by varying the composition of natural dye from moss chlorophyll (Bryophyte) and synthesis dye from ruthenium complex N719. The sandwich structure of DSSC consists of the working electrode using TiO2, dye, electrolyte, and counter electrode using carbon. The composition of chlorophyll and synthesis dyes mixture were 100% and 0%, 80% and 20%, 60% and 40%, 40% and 60%, and 20% and 80%. The UV-Vis absorption spectra of moss chlorophyll showed the first peak in the wavelength range of 450-500 nm and the second peak at wavelength of 650-700 nm. The peak value of absorbance at wavelengths of 450-500 nm was 6.1004 and at wavelengths of 650-700 nm was 3.5835. The IPCE characteristic curves showed the absorption peak of photon for DSSCs occurred at wavelength of 550-650 nm. It considered that photon in this wavelength can contribute dominantly to produce the optimum electrons. The I-V characteristics of DSSCs with composition of chlorophyll and synthesis dyes mixture of 100% and 0%, 80% and 20%, 60% and 40%, 40% and 60%, and 20% and 80% resulted the efficiency of 0.0022; 0.0194; 0.0239; 0.0342; and 0.0414, respectively. It suggested that the addition of a little composition of the ruthenium complex dye into moss chlorophyll dye can increase the efficiency significantly.

Performance and stability analysis of curcumin dye as a photo sensitizer used in nanostructured ZnO based DSSC

NASA Astrophysics Data System (ADS)

Sinha, D.; De, D.; Ayaz, A.

2018-03-01

Environmental friendly natural dye curcumin extracted from low-cost Curcumina longa stem is used as a photo-sensitizer for the fabrication of ZnO-based dye-sensitized solar cells (DSSC). Nanostructured ZnO is fabricated on a transparent conducting glass (TCO), using a cost-effective chemical bath deposition technique. Scanning electron microscopic images show hexagonal patterned ZnO nano-towers decorated with several nanosteps. The average length of ZnO nano-tower is 5 μm and diameter is 1.2 μm. The UV-Vis spectroscopic study of the curcumin dye is used to understand the light absorption behavior as well as band gap energy of the extracted natural dye. The dye shows wider absorption band-groups over 350-470 nm and 500-600 nm with two peaks positioned at 425 nm and 525 nm. The optical band gap energy and energy band position of the dye is derived which supports its stability and high electron affinity that makes it suitable for light harvesting and effortless electron transfer from dye to the semiconductor or interface between them. FTIR spectrum of curcumin dye-sensitized ZnO-based DSSC shows the presence of anchoring groups and colouring constitutes. The I-V and P-V curves of the fabricated DSSC are measured under simulated light (100 mW/cm2). The highest visible light to electric conversion efficiency of 0.266% (using ITO) and 0.33% (using FTO) is achieved from the curcumin dye-sensitized cell.

Chemotaxis of Molecular Dyes in Polymer Gradients in Solution.

PubMed

Guha, Rajarshi; Mohajerani, Farzad; Collins, Matthew; Ghosh, Subhadip; Sen, Ayusman; Velegol, Darrell

2017-11-08

Chemotaxis provides a mechanism for directing the transport of molecules along chemical gradients. Here, we show the chemotactic migration of dye molecules in response to the gradients of several different neutral polymers. The magnitude of chemotactic response depends on the structure of the monomer, polymer molecular weight and concentration, and the nature of the solvent. The mechanism involves cross-diffusion up the polymer gradient, driven by favorable dye-polymer interaction. Modeling allows us to quantitatively evaluate the strength of the interaction and the effect of the various parameters that govern chemotaxis.

Other origins for the fluorescence modulation of single dye molecules in open-circuit and short-circuit devices.

PubMed

Teguh, Jefri S; Kurniawan, Michael; Wu, Xiangyang; Sum, Tze Chien; Yeow, Edwin K L

2013-01-07

Fluorescence intensity modulation of single Atto647N dye molecules in a short-circuit device and a defective device, caused by damaging an open-circuit device, is due to a variation in the excitation light focus as a result of the formation of an alternating electric current.

Investigation on Large Molecule Permeation through Liposome Lipid Bilayer Induced by Microplasma Irradiation

NASA Astrophysics Data System (ADS)

Nagaiwa, Hidenori; Aibara, Daijiro; Ikeda, Yoshihisa; Motomura, Hideki; Kido, Yugo; Satoh, Susumu; Tachibana, Kunihide; Jinno, Masahumi

2015-09-01

The authors have been developing a novel gene transfection method using microplasma irradiation. In order to clarify the mechanism of large molecule permeation process through the lipid bilayer, plasma induced outflow of hydrophilic fluorescent dye molecules, which were encapsulated in the liposome, was observed. By microplasma irradiation on the liposome suspension, the dyes flowed out from the inside of the liposomes. The outflow of the dyes was enhanced by longer plasma irradiation time. Investigation of the outflow mechanism, i.e. permeation enhancement of the lipid bilayer or burst of the liposome, is under progress. This work was partly supported by JSPS KAKENHI Grant-in-Aid for Scientific Research on Innovative Areas (Number 25108509,15H00896) and a grant from Ehime University.

Directional emission from dye-functionalized plasmonic DNA superlattice microcavities

PubMed Central

Park, Daniel J.; Ku, Jessie C.; Sun, Lin; Lethiec, Clotilde M.; Stern, Nathaniel P.; Schatz, George C.; Mirkin, Chad A.

2017-01-01

Three-dimensional plasmonic superlattice microcavities, made from programmable atom equivalents comprising gold nanoparticles functionalized with DNA, are used as a testbed to study directional light emission. DNA-guided nanoparticle colloidal crystallization allows for the formation of micrometer-scale single-crystal body-centered cubic gold nanoparticle superlattices, with dye molecules coupled to the DNA strands that link the particles together, in the form of a rhombic dodecahedron. Encapsulation in silica allows one to create robust architectures with the plasmonically active particles and dye molecules fixed in space. At the micrometer scale, the anisotropic rhombic dodecahedron crystal habit couples with photonic modes to give directional light emission. At the nanoscale, the interaction between the dye dipoles and surface plasmons can be finely tuned by coupling the dye molecules to specific sites of the DNA particle-linker strands, thereby modulating dye–nanoparticle distance (three different positions are studied). The ability to control dye position with subnanometer precision allows one to systematically tune plasmon–excition interaction strength and decay lifetime, the results of which have been supported by electrodynamics calculations that span length scales from nanometers to micrometers. The unique ability to control surface plasmon/exciton interactions within such superlattice microcavities will catalyze studies involving quantum optics, plasmon laser physics, strong coupling, and nonlinear phenomena. PMID:28053232

Choosing the right fluorophore for single-molecule fluorescence studies in a lipid environment.

PubMed

Zhang, Zhenfu; Yomo, Dan; Gradinaru, Claudiu

2017-07-01

Nonspecific interactions between lipids and fluorophores can alter the outcomes of single-molecule spectroscopy of membrane proteins in live cells, liposomes or lipid nanodiscs and of cytosolic proteins encapsulated in liposomes or tethered to supported lipid bilayers. To gain insight into these effects, we examined interactions between 9 dyes that are commonly used as labels for single-molecule fluorescence (SMF) and 6 standard lipids including cationic, zwitterionic and anionic types. The diffusion coefficients of dyes in the absence and presence of set amounts of lipid vesicles were measured by fluorescence correlation spectroscopy (FCS). The partition coefficients and the free energies of partitioning for different fluorophore-lipid pairs were obtained by global fitting of the titration FCS curves. Lipids with different charges, head groups and degrees of chain saturation were investigated, and interactions with dyes are discussed in terms of hydrophobic, electrostatic and steric contributions. Fluorescence imaging of individual fluorophores adsorbed on supported lipid bilayers provides visualization and additional quantification of the strength of dye-lipid interaction in the context of single-molecule measurements. By dissecting fluorophore-lipid interactions, our study provides new insights into setting up single-molecule fluorescence spectroscopy experiments with minimal interference from interactions between fluorescent labels and lipids in the environment. Copyright © 2017 Elsevier B.V. All rights reserved.

Preparation and Optimization of Fluorescent Thin Films of Rosamine-SiO2/TiO2 Composites for NO2 Sensing

PubMed Central

Guillén, María G.; Gámez, Francisco; Suárez, Belén; Queirós, Carla; Silva, Ana M. G.; Barranco, Ángel; Sánchez-Valencia, Juan Ramón; Pedrosa, José María; Lopes-Costa, Tânia

2017-01-01

The incorporation of a prototypical rosamine fluorescent dye from organic solutions into transparent and microstructured columnar TiO2 and SiO2 (MO2) thin films, prepared by evaporation at glancing angles (GAPVD), was evaluated. The aggregation of the adsorbed molecules, the infiltration efficiency and the adsorption kinetics were studied by means of UV-Vis absorption and fluorescence spectroscopies. Specifically, the infiltration equilibrium as well as the kinetic of adsorption of the emitting dye has been described by a Langmuir type adsorption isotherm and a pseudosecond order kinetic model, respectively. The anchoring mechanism of the rosamine to the MO2 matrix has been revealed by specular reflectance Fourier transform infrared spectroscopy and infiltration from aqueous solutions at different pH values. Finally, the sensing performance towards NO2 gas of optimized films has been assessed by following the changes of its fluorescence intensity revealing that the so-selected device exhibited improved sensing response compared to similar hybrid films reported in the literature. PMID:28772484

Photovoltaic Devices Prepared through a Trihydroxy Substitution Strategy on an Unsymmetrical Squaraine Dye.

PubMed

Wu, Jianglin; Si, Changfeng; Chen, Yao; Yang, Lin; Hu, Bin; Chen, Guo; Lu, Zhiyun; Huang, Yan

2018-03-02

A series of unsymmetrical arene-1,3-squaraine (USQ) derivatives with two, three, or four hydroxy (-OH) substituents, namely, USQ-2-OH, USQ-3-OH, or USQ-4-OH, respectively, were designed and synthesized, and the effect of the number of hydroxy groups on the optoelectronic properties of USQs were investigated. Despite the three compounds having similar UV/Vis absorption and HOMO energy levels, solution-processed bulk-heterojunction (BHJ) small-molecule organic solar cells with USQ-3-OH as electron-donor materials exhibit the highest power conversion efficiency of 6.07 %, which could be mainly attributed to the higher hole mobility and smaller phase separation. It is also noteworthy that the short-circuit current (J sc ) of the USQ-3-OH-based device is as high as 14.95 mA cm -2 , which is the highest J sc values reported for squaraine-based BHJ solar cells to date. The results also indicate that more -OH substituents on squaraine dyes do not necessarily lead to better photovoltaic performance. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Efficiency Selective Electron Tunnelling in a Heterostructure Photovoltaic Diode.

PubMed

Jia, Chuancheng; Ma, Wei; Gu, Chunhui; Chen, Hongliang; Yu, Haomiao; Li, Xinxi; Zhang, Fan; Gu, Lin; Xia, Andong; Hou, Xiaoyuan; Meng, Sheng; Guo, Xuefeng

2016-06-08

A heterostructure photovoltaic diode featuring an all-solid-state TiO2/graphene/dye ternary interface with high-efficiency photogenerated charge separation/transport is described here. Light absorption is accomplished by dye molecules deposited on the outside surface of graphene as photoreceptors to produce photoexcited electron-hole pairs. Unlike conventional photovoltaic conversion, in this heterostructure both photoexcited electrons and holes tunnel along the same direction into graphene, but only electrons display efficient ballistic transport toward the TiO2 transport layer, thus leading to effective photon-to-electricity conversion. On the basis of this ipsilateral selective electron tunnelling (ISET) mechanism, a model monolayer photovoltaic device (PVD) possessing a TiO2/graphene/acridine orange ternary interface showed ∼86.8% interfacial separation/collection efficiency, which guaranteed an ultrahigh absorbed photon-to-current efficiency (APCE, ∼80%). Such an ISET-based PVD may become a fundamental device architecture for photovoltaic solar cells, photoelectric detectors, and other novel optoelectronic applications with obvious advantages, such as high efficiency, easy fabrication, scalability, and universal availability of cost-effective materials.

Ag@Aggregation-induced emission dye core/shell nanostructures with enhanced one- and two-photon fluorescence

NASA Astrophysics Data System (ADS)

Wang, Cheng; Li, Yang; Xu, Qiujin; Luo, Liang

2017-10-01

Combining plasmonic nanostructures with two-photon fluorescence materials is a promising way to significantly enhance two-photon fluorescence. Ag@1,4-bis(2-cyano-2-phenylethenyl) benzene (BCPEB) core/shell nanostructures were fabricated by simply incubating the isolated Ag nanoparticles with BCPEB microrods in ethanol. BCPEB was chosen as the fluorescent organic molecule owing to the aggregation-induced-emission (AIE) nature which would reduce the emission loss as being practically applied in solid phase. By utilizing the match of the extinction spectrum of Ag nanoparticles and BCPEB's absorption band, the target Ag@BCPEB core/shell nanostructures showed an enhanced one-photon (12×) fluorescence, integrating with SERS signal as well. Moreover, the resultant second harmonic generation of Ag nanoparticles under two-photon excitation also well matched with the absorption band of BCPEB, and significant enhanced two-photon (17×) fluorescence was obtained. The confocal images of NIH-3T3 cells with these nanostructures under one- and two-photon excitation showed good contrast and brightness for bio-imaging.

Altering the self-organization of dyes on titania with dyeing solvents to tune the charge-transfer dynamics of sensitized solar cells.

PubMed

Wang, Yinglin; Yang, Lin; Zhang, Jing; Li, Renzhi; Zhang, Min; Wang, Peng

2014-04-14

Herein we selected the model organic donor-acceptor dye C218 and modulated the self-organization of dye molecules on the surface of titania by changing the dyeing solvent from chlorobenzene to a mixture of acetonitrile and tert-butanol. We further unveiled the relationship between the microstructure of a dye layer and the multichannel charge-transfer dynamics that underlie the photovoltaic performance of dye-sensitized solar cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-Normalized Photoacoustic Technique for the Quantitative Analysis of Paper Pigments

NASA Astrophysics Data System (ADS)

Balderas-López, J. A.; Gómez y Gómez, Y. M.; Bautista-Ramírez, M. E.; Pescador-Rojas, J. A.; Martínez-Pérez, L.; Lomelí-Mejía, P. A.

2018-03-01

A self-normalized photoacoustic technique was applied for quantitative analysis of pigments embedded in solids. Paper samples (filter paper, Whatman No. 1), attached with the pigment: Direct Fast Turquoise Blue GL, were used for this study. This pigment is a blue dye commonly used in industry to dye paper and other fabrics. The optical absorption coefficient, at a wavelength of 660 nm, was measured for this pigment at various concentrations in the paper substrate. It was shown that Beer-Lambert model for light absorption applies well for pigments in solid substrates and optical absorption coefficients as large as 220 cm^{-1} can be measured with this photoacoustic technique.

A Simple Parallel Photochemical Reactor for Photodecomposition Studies

ERIC Educational Resources Information Center

Xiaobo Chen; Halasz, Sarah M.; Giles, Eric C.; Mankus, Jessica V.; Johnson, Joseph C.; Burda, Clemens

2006-01-01

A simple and useful parallel photochemical reactor intended to study the photodecomposition of dyes using semiconductor photocatalysis is presented. The photochemical reactions are followed through time-dependent changes in the ground-state absorption spectra of the dyes.

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.

Performance optimization of dye-sensitized solar cells by multilayer gradient scattering architecture of TiO2 microspheres.

PubMed

Li, Mingyue; Li, Meiya; Liu, Xiaolian; Bai, Lihua; Luoshan, Mengdai; Lei, Wen; Wang, Zhen; Zhu, Yongdan; Zhao, Xingzhong

2017-01-20

TiO 2 microspheres (TMSs) with unique hierarchical structure and unusual high specific surface area are synthesized and incorporated into a photoanode in various TMS multilayer gradient architectures to form novel photoanodes and dye-sensitized solar cells (DSSCs). Significant influences of these architectures on the photoelectric properties of DSSCs are obtained. The DSSC with the optimal TMS gradient-ascent architecture of M036 has the largest amounts of dye absorption, strongest light absorption, longest electron lifetime and lowest electron recombination, and thus exhibits the maximum short circuit current density (J sc ) of 16.49 mA cm -2 and photoelectric conversion efficiency (η) of 7.01%, notably higher than those of conventional DSSCs by 21% and 22%, respectively. These notable improvements in the properties of DSSCs can be attributed to the TMS gradient-ascent architecture of M036 which can most effectively increase dye absorption and localize incident light within the photoanode by the light scattering of TMSs, and thus utilize the incident light thoroughly. This study provides an optimized and universal configuration for the scattering microspheres incorporated in the hybrid photoanode, which can significantly improve the performance of DSSCs.

Characterization of domain-specific interaction of synthesized dye with serum proteins by spectroscopic and docking approaches along with determination of in vitro cytotoxicity and antiviral activity.

PubMed

Rudra, Suparna; Dasmandal, Somnath; Patra, Chiranjit; Patel, Biman Kumar; Paul, Suvendu; Mahapatra, Ambikesh

2017-11-20

The interaction between a synthesized dye with proteins, bovine, and human serum albumin (BSA, HSA, respectively) under physiological conditions has been characterized in detail, by means of steady-state and time-resolved fluorescence, UV-vis absorption, and circular dichroism (CD) techniques. An extensive time-resolved fluorescence spectroscopic characterization of the quenching process has been undertaken in conjugation with temperature-dependent fluorescence quenching studies to divulge the actual quenching mechanism. From the thermodynamic observations, it is clear that the binding process is a spontaneous molecular interaction, in which van der Waals and hydrogen bonding interactions play the major roles. The UV-vis absorption and CD results confirm that the dye can induce conformational and micro-environmental changes of both the proteins. In addition, the dye binding provokes the functionality of the native proteins in terms of esterase-like activity. The average binding distance (r) between proteins and dye has been calculated using FRET. Cytotoxicity and antiviral effects of the dye have been found using Vero cell and HSV-1F virus by performing MTT assay. The AutoDock-based docking simulation reveals the probable binding location of dye within the sub-domain IIA of HSA and IB of BSA.

Improvement of photovoltaic performance by substituent effect of donor and acceptor structure of TPA-based dye-sensitized solar cells.

PubMed

Inostroza, Natalia; Mendizabal, Fernando; Arratia-Pérez, Ramiro; Orellana, Carlos; Linares-Flores, Cristian

2016-01-01

We report a computational study of a series of organic dyes built with triphenylamine (TPA) as an electron donor group. We designed a set of six dyes called (TPA-n, where n = 0-5). In order to enhance the electron-injection process, the electron-donor effect of some specific substituent was studied. Thus, we gave insights into the rational design of organic TPA-based chromophores for use in dye-sensitized solar cells (DSSCs). In addition, we report the HOMO, LUMO, the calculated excited state oxidized potential E(dye*)(eV) and the free energy change for electron-injection ΔGinject(eV), and the UV-visible absorption bands for TPA-n dyes by a time-dependent density functional theory (TDDFT) procedure at the B3LYP and CAM-B3LYP levels with solvent effect. The results demonstrate that the introduction of the electron-acceptor groups produces an intramolecular charge transfer showing a shift of the absorption wavelengths of TPA-n under studies. Graphical Abstract Several organic dyes TPA-n with different donors and acceptors are modeled. A strong conjugation acrros the donor and anchoring groips (TPA-n) bas been studied. Candidate TPA-3 shows a promising results.

Electrodeposited styrylquinolinium dye as molecular electrocatalyst for coupled redox reactions.

PubMed

Hubenova, Yolina; Bakalska, Rumyana; Mitov, Mario

2018-05-10

Modification of carbonaceous materials with different conductive coatings is a successful approach to enhance their electrocatalytic activity and thus to increase the electrical outputs when used as electrodes in biofuel cells. In this study, a methodology for electrodeposition of styrylquinolinium dye on carbon felt was developed. The produced dye electrodeposits were characterized by means of AFM, ESI-MS/MS and NMR spectroscopy. The obtained data reveal that the dye forms overlaid layers consisting of monomer molecules most likely with an antiparallel orientation. The UV-VIS spectroscopy, CV and EIS analyses show that the dye molecules preserve their redox activity within the coating and a charge transfer between NADH/NAD + and electrodeposit is possible as a coupled redox reaction. The fabricated nano-modified electrodes were also tested as anodes in batch-mode operating yeast-based biofuel cell. The results indicate that the electrodeposited dye acts as an immobilized exogenous mediator, contributing to enhanced extracellular electron transfer. Copyright © 2018. Published by Elsevier B.V.

Colorant modelling for on-line paper coloring: Evaluations of models and an extension to Kubelka-Munk model

NASA Astrophysics Data System (ADS)

Shakespeare, Tarja Tuulikki

Traditionally, single constant Kubelka-Munk type colorant formulation algorithms have been used for color control in the paper industry. Tuning data is derived from colored handsheets representing dyeing of a particular color grade, applicable to a substrate of similar properties. Due to furnish variation and changes in the chemical environment, such tuning data is of limited accuracy in practice. Kubelka-Munk approaches have numerous other limitations, in part due to their physically unrealistic assumptions. In particular, they neglect fluorescence phenomena, the interdependence of absorption and scattering, and nonlinearities due to colorant interactions. This thesis addresses those problems. A set of colored handsheets was made, employing several anionic direct dyes and fluorescent colorants, individually and in various combinations. Both a spectrophotometer and a spectrofluorimeter were used for measuring color properties. An extended Langmuir adsorption isotherm was used in modelling the dye-on- fiber in each dyeing. Kubelka-Munk absorption and scattering coefficients were then modelled based on dye- on-fiber, and a number of the limitations of the Kubelka- Munk approach were clearly demonstrated. An extended phenomenological model was derived, incorporating fluorescence and interdependence of absorption and scattering. This model predicts illuminator-independent radiance transfer factors based on dye-on-fiber, from which total radiance factor responses under arbitrary illumination can be computed. It requires spectrofluorometric measurements to characterize the coloring process. A new reflectance factor model, based on the same adsorption isotherm approach, was derived for non- fluorescent colorants. A corresponding total radiance factor model, which is illuminator-dependent, was derived for fluorescent colorants. These models have provision for phenomena such as broadening of absorption and scattering bands, which are encountered in practice. Being based on spectrophotometric measurements, they are directly applicable in industrial settings, and predict colorant responses reliably under wider ranges of conditions than the Kubelka-Munk approach.

N,N'-Bis((6-methoxylpyridin-2-yl)methylene)-p-phenylenediimine based d(10) transition metal complexes and their utilization in co-sensitized solar cells.

PubMed

Wei, Liguo; Yang, Yulin; Fan, Ruiqing; Na, Yong; Wang, Ping; Dong, Yuwei; Yang, Bin; Cao, Wenwu

2014-08-07

N,N'-Bis((6-methoxylpyridin-2-yl)methylene)-p-phenylenediimine based four-coordinated d(10) transition metal complexes (named ML, M = Zn, Cd, Hg) were synthesized and employed as co-sensitizers and co-adsorbents in combination with a ruthenium complex N719 in dye sensitized solar cells. After co-sensitization, not only the incident-photon-to-current conversion efficiency is enhanced but also the dark current is reduced. A short circuit current density of 14.46 mA cm(-2), an open circuit voltage of 0.74 V and a fill factor of 0.62 corresponding to an overall conversion efficiency of 6.65% under AM 1.5 G solar irradiation were achieved when ZnL was used as a co-sensitizer, which are much higher than that for DSSCs only sensitized by N719 (5.22%) under the same conditions. The improvement in efficiency is attributed to the fact that N,N'-bis((6-methoxylpyridin-2-yl)methylene)-p-phenylenediimine coordinated complexes overcome the deficiency of N719 absorption in the low wavelength region of the visible spectrum, prevent its aggregation, offset competitive visible light absorption of I3(-) and reduce charge recombination due to formation of an effective cover layer of the dye molecules on the TiO2 surface. As a result, the synthesized complexes are promising candidates as co-adsorbents and co-sensitizers for highly efficient DSSCs.

Spectral Fluorescence Properties of an Anionic Oxacarbocyanine Dye in Complexes with Human Serum Albumin

NASA Astrophysics Data System (ADS)

Pronkin, P. G.; Tatikolov, A. S.

2015-07-01

The spectral fluorescence properties of the anionic oxacarbocyanine dye 3,3'-di-(γ-sulfopropyl)-5,5'-diphenyl-9-ethyloxacarbocyanine betaine (OCC) were studied in solutions and in complexes with human serum albumin (HSA). Interaction with HSA leads to a significant increase in the fluorescence of the dye. We studied quenching of the fluorescence of OCC in a complex with HSA by ibuprofen and warfarin. Data on quenching of fluorescence by ibuprofen indicate binding of the dye to binding site II of subdomain IIIA in the HSA molecule. Synchronous fluorescence spectra of human serum albumin in the presence of OCC showed that complexation with OCC does not lead to appreciable rearrangement of the protein molecule at the binding site.

Nanoneedle transistor-based sensors for the selective detection of intracellular calcium ions.

PubMed

Son, Donghee; Park, Sung Young; Kim, Byeongju; Koh, Jun Tae; Kim, Tae Hyun; An, Sangmin; Jang, Doyoung; Kim, Gyu Tae; Jhe, Wonho; Hong, Seunghun

2011-05-24

We developed a nanoneedle transistor-based sensor (NTS) for the selective detection of calcium ions inside a living cell. In this work, a single-walled carbon nanotube-based field effect transistor (swCNT-FET) was first fabricated at the end of a glass nanopipette and functionalized with Fluo-4-AM probe dye. The selective binding of calcium ions onto the dye molecules altered the charge state of the dye molecules, resulting in the change of the source-drain current of the swCNT-FET as well as the fluorescence intensity from the dye. We demonstrated the electrical and fluorescence detection of the concentration change of intracellular calcium ions inside a HeLa cell using the NTS.

Trapping characteristic of halloysite lumen for methyl orange

NASA Astrophysics Data System (ADS)

Chen, Hao; Yan, Hua; Pei, Zhenzhao; Wu, Junyong; Li, Rongrong; Jin, Yanxian; Zhao, Jie

2015-08-01

The interaction of clay minerals and dyes is an area of great interest especially in the development of novel adsorbents. In this report, we demonstrated interaction of halloysite nanotubes (HNTs) and an anionic dye, methyl orange (MO), through a electrostatic attraction. Halloysite lumen has a trapping characteristic for methyl orange, which is mainly determined by the positively charged nature of the inner surface of HNTs. XRD results confirmed that intercalation of methyl orange into HNTs did not occur. SEM-EDS and photostability results showed that MO molecules were primarily in HNTs lumen. Adsorption isotherm studies revealed an interesting phenomenon, i.e., a sudden increase of adsorption capacity occurred in the initial dye concentration of about 75 mg/L, which was just the dye concentration corresponding to the onset of dye oligomer formation. This suggested dye aggregation state had a decisive influence to the adsorption behavior of MO on the halloysite. BET results demonstrated at low and high dye concentrations, single MO molecule and aggregation of several dimers through hydrophobic interaction, interacted with Al-OH2+ sites on the inner wall, respectively. Desorption experiments showed that MO in HNTs can be completely removed with deionized water, indicating halloysite is a low-cost and efficient adsorbent for anionic dye.

Metachromasy: An Experimental and Theoretical Reevaluation

PubMed Central

Bergeron, John A.; Singer, Marcus

1958-01-01

Non-chromotropic substances such as fibrin and gelatin and most tissue and cellular structures stain orthochromatically with internal dye concentrations of such metachromatic dyes as methylene blue and toluidine blue which, if in solution, would be metachromatic. Therefore, at ordinary levels of staining these substances depress the natural tendency of these dyes to change color. However, at elevated levels of dye-binding metachromasy eventually occurs. This phenomenon is explained on the basis of the distribution of dye-binding sites. In these substrates, by contrast with chromotropic substances, many binding sites are too far removed for dye interaction, consequently the interaction frequency can become high enough to produce a color change only as saturation of the available sites is approached. It is also shown that the destruction of color is a characteristic of metachromasy and that water molecules intercalated between approximated dye ions are responsible for the loss and change of color. A concept of metachromasy is proposed in which the interaction between water molecules and suitably approximated dye ions plays an essential role. The experimental studies are described against a background of the history and evolution of ideas on metachromasy. The literature is reviewed and reassessed particularly from the physicochemical viewpoint. PMID:13563551

Kinetic and calorimetric study of the adsorption of dyes on mesoporous activated carbon prepared from coconut coir dust.

PubMed

Macedo, Jeremias de Souza; da Costa Júnior, Nivan Bezerra; Almeida, Luis Eduardo; Vieira, Eunice Fragoso da Silva; Cestari, Antonio Reinaldo; Gimenez, Iara de Fátima; Villarreal Carreño, Neftali Lênin; Barreto, Ledjane Silva

2006-06-15

Mesoporous activated carbon has been prepared from coconut coir dust as support for adsorption of some model dye molecules from aqueous solutions. The methylene blue (MB) and remazol yellow (RY) molecules were chosen for study of the adsorption capacity of cationic and anionic dyes onto prepared activated carbon. The adsorption kinetics was studied with the Lagergren first- and pseudo-second-order kinetic models as well as the intraparticle diffusion model. The results for both dyes suggested a multimechanism sorption process. The adsorption mechanisms in the systems dyes/AC follow pseudo-second-order kinetics with a significant contribution of intraparticle diffusion. The samples simultaneously present acidic and basic sites able to act as anchoring sites for basic and acidic dyes, respectively. Calorimetric studies reveal that dyes/AC interaction forces are correlated with the pH of the solution, which can be related to the charge distribution on the AC surface. These AC samples also exhibited very short equilibrium times for the adsorption of both dyes, which is an economically favorable requisite for the activated carbon described in this work, in addition to the local abundance of the raw material.

Theoretical structures and binding energies of RNA-RNA/cyanine dyes and spectroscopic properties of cyanine dyes

NASA Astrophysics Data System (ADS)

Salaeh, Salsabila; Chong, Wei Lim; Dokmaisrijan, Supaporn; Payaka, Apirak; Yana, Janchai; Nimmanpipug, Piyarat; Lee, Vannajan Sanghiran; Dumri, Kanchana; Anh, Dau Hung

2014-10-01

Cyanine dyes have been widely used as a fluorescence probe for biomolecules and protein labeling. The mostly used cyanine dyes for nucleic acids labeling are DiSC2(3), DiSC2(5), and DiSC2(7). The possible structures and binding energies of RNA-RNA/Cyanine dyes were predicted theoretically using AutoDock Vina. The results showed that cyanine dyes and bases of RNA-RNA have the van der Waals and pi-pi interactions. The maximum absorption wavelength in the visible region obtained from the TD-DFT calculations of all cyanine dyes in the absence of the RNA-RNA double strand showed the bathochromic shift.

Organic Semiconductors based on Dyes and Color Pigments.

PubMed

Gsänger, Marcel; Bialas, David; Huang, Lizhen; Stolte, Matthias; Würthner, Frank

2016-05-01

Organic dyes and pigments constitute a large class of industrial products. The utilization of these compounds in the field of organic electronics is reviewed with particular emphasis on organic field-effect transistors. It is shown that for most major classes of industrial dyes and pigments, i.e., phthalocyanines, perylene and naphthalene diimides, diketopyrrolopyrroles, indigos and isoindigos, squaraines, and merocyanines, charge-carrier mobilities exceeding 1 cm(2) V(-1) s(-1) have been achieved. The most widely investigated molecules due to their n-channel operation are perylene and naphthalene diimides, for which even values close to 10 cm(2) V(-1) s(-1) have been demonstrated. The fact that all of these π-conjugated colorants contain polar substituents leading to strongly quadrupolar or even dipolar molecules suggests that indeed a much larger structural space shows promise for the design of organic semiconductor molecules than was considered in this field traditionally. In particular, because many of these dye and pigment chromophores demonstrate excellent thermal and (photo-)chemical stability in their original applications in dyeing and printing, and are accessible by straightforward synthetic protocols, they bear a particularly high potential for commercial applications in the area of organic electronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectral Changes of Erythrosin B Luminescence Upon Binding to Bovine Serum Albumin

NASA Astrophysics Data System (ADS)

Sablin, N. V.; Gerasimova, M. A.; Nemtseva, E. V.

2016-04-01

Changes in absorption, fluorescence, phosphorescence, and delayed fluorescence spectra of erythrosin B are studied in the presence of bovine serum albumin at room temperature. Spectral and chronoscopic characteristics of the observed photophysical processes are defined. The binding of erythrosin B with the protein followed by spectral changes is demonstrated. Absorption and fluorescence spectra of the dye in the bound state are described, the binding mechanism is analyzed. The binding parameters of the dye-protein complex are estimated.

Single-crystal films of a combination of materials (co-crystal) involving DAST and IR-125 for electro-optic applications

NASA Astrophysics Data System (ADS)

Narayanan, A.; Titus, J.; Rajagopalan, H.; Vippa, P.; Thakur, M.

2006-03-01

Single-crystal film of DAST (4'-dimethylamino-N-methyl-4-stilbazolium tosylate) has been shown [1] to have exceptionally large electro-optic coefficients (r11 ˜ 770 pm/V at 633 nm). In this report, single crystal film of a combination of materials (co-crystal) involving DAST and a dye molecule IR-125 will be discussed. Modified shear method was used to prepare the co-crystal films. The film has been characterized using polarized optical microscopy, optical absorption spectroscopy and x-ray diffraction. The optical absorption spectrum has two major bands: one at about 350--600 nm corresponding to DAST and the other at about 600-900 nm corresponding to IR-125. The x-ray diffraction results show peaks involving the presence of DAST and IR-125 within the co-crystal film. Since the co-crystal has strong absorption at longer wavelengths it is expected to show higher electro-optic coefficients at longer wavelengths. Preliminary measurements at 1.55 μm indicate a high electro-optic coefficient of the co-crystal film. [1] Swamy, Kutty, Titus, Khatavkar, Thakur, Appl. Phys. Lett. 2004, 85, 4025; Kutty, Thakur, Appl. Phys. Lett. 2005, 87, 191111.

Adsorption mechanism for xanthene dyes to cellulose granules.

PubMed

Tabara, Aya; Yamane, Chihiro; Seguchi, Masaharu

2012-01-01

The xanthene dyes, erythrosine, phloxine, and rose bengal, were adsorbed to charred cellulose granules. The charred cellulose granules were preliminarily steeped in ionic (NaOH, NaCl, KOH, KCl, and sodium dodecyl sulfate (SDS)), nonionic (glucose, sucrose, and ethanol), and amphipathic sucrose fatty acid ester (SFAE) solutions, and adsorption tests on the dye to the steeped and charred cellulose granules were conducted. Almost none of the dye was adsorbed when the solutions of ionic and amphipathic molecules were used, but were adsorbed in the case of steeping in the nonionic molecule solutions. Thin-layer chromatography (TLC) and the Fourier transform infra-red (FT-IR) profiles of SFAE which was adsorbed to the charred cellulose granules and extracted by ethyl ether suggested the presence of hydrophobic sites on the surface of the charred cellulose granules. We confirmed that the xanthene dyes could bind to the charred cellulose granules by ionic and hydrophobic bonds.

Development of UV-curable liquid for in-liquid fluorescence alignment in ultraviolet nanoimprint lithography

NASA Astrophysics Data System (ADS)

Ochiai, Kento; Kikuchi, Eri; Ishito, Yota; Kumagai, Mari; Nakamura, Takahiro; Nakagawa, Masaru

2018-06-01

We studied a fluorescent UV-curable resin suitable for fluorescence alignment in UV nanoimprinting. The addition of a cationic fluorescent dye caused radical photopolymerization of a UV-curable resin by exposure to visible excitation light for fluorescence microscope observation. The microscope observation of a resin film prepared by pressing resin droplets on a silica substrate with a fluorinated silica superstrate revealed that the cationic dye molecules were preferably adsorbed onto the silica surface. It was indicated that the dye molecules concentrated on the silica surface may cause the photocuring. A nonionic fluorescent dye was selected owing to its low polar symmetrical structure and its solubility parameter close to monomers. The fluorescent UV-curable resin with the nonionic dye showed uncured stability to exposure to visible excitation light for 30 min with a light intensity of 8.5 mW cm‑2 detected at 530 nm.

Shaving effects on percutaneous penetration: clinical implications.

PubMed

Hamza, Muhammad; Tohid, Hassaan; Maibach, Howard

2015-01-01

Human/animal shaving biology. To assess the effect of shaving on percutaneous penetration and skin function. We screened 500+publications in Pub Med, Scopus, Cochrane Library and pertinent journals out of which only 17 were deemed relevant. Terms for searches included shaving and skin, percutaneous penetration and shaving, skin absorption and shaving, absorption of dyes and shaving, skin penetration, effects of shaving and absorption, shave and dyes, axillary shaving and stratum corneum, shaving and breast cancer, shaving and infections, etc. Shaving appears to have an exaggerated effect on percutaneous absorption; however, some studies do not support this evidence. Shaving enhances percutaneous penetration of some chemicals; however this effect is species and chemical specific. Further investigations of chemicals of varying physio-chemical properties are mandated before a generalized theory can be promulgated.

Fabrication of a dye-doped liquid crystal light shutter by thermal curing of polymer

NASA Astrophysics Data System (ADS)

Yu, Byeong-Hun; Ji, Seong-Min; Kim, Jin-Hun; Huh, Jae-Won; Yoon, Tae-Hoon

2017-07-01

We report a thermal curing method for fabrication of a dye-doped polymer-stabilized liquid crystal (PSLC) light shutter, which can prevent the decrease in absorption and discoloration of the dye caused by the UV curing process. We found that the measured transmittance in the opaque state of a dye-doped PSLC cell fabricated by thermal curing was approximately 35% lower than that of a dye-doped PSLC cell fabricated by UV curing. Thermal curing can be an alternative approach for fabrication of a dye-doped PSLC light shutter which can be used to provide high visibility of a see-through display.

Green Perylene Bisimide Dyes: Synthesis, Photophysical and Electrochemical Properties

PubMed Central

Chang, Che-Wei; Tsai, Hsing-Yang; Chen, Kew-Yu

2014-01-01

Three asymmetric amino-substituted perylene bisimide dyes with different n-alkyl chain lengths (n = 6, 12, or 18), 1-(N,N-dialkylamino)perylene bisimides (1a–1c), were synthesized under mild condition in high yields and were characterized by 1H NMR, 13C NMR (nuclear magnetic resonance), HRMS (High Resolution Mass Spectrometer), UV-Vis and fluorescence spectra, as well as cyclic voltammetry (CV). These molecules show intense green color in both solution and solid state and are highly soluble in dichloromethane and even in nonpolar solvents, such as hexane. The shapes of the absorption spectra of 1a–1c in solid state and in solution were found to be virtually the same, indicating that the long alkyl chains could efficiently prevent aggregation. They exhibit a unique charge transfer emission in the near-infrared region, of which the peak wavelengths show strong solvatochromism. The dipole moments of the compounds have been estimated using the Lippert-Mataga equation, and upon excitation, they show larger dipole moment changes than that of 1-aminoperylene bisimide (2). Furthermore, all of the compounds exhibit two quasi-reversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory (DFT) calculations performed on these dyes are reported in order to rationalize their molecular structures and electronic properties. PMID:28788140

A high resolution spectroscopic study of the oxygen molecule. Ph.D. Thesis Final Report

NASA Technical Reports Server (NTRS)

Ritter, K. J.

1984-01-01

A high resolution spectrometer which incorporates a narrow line width tunable dye laser was used to make absorption profiles of 57 spectral lines in the Oxygen A-Band at pressures up to one atmosphere in pure O2. The observed line profiles are compared to the Voigt, and a collisionally narrowed, profile using a least squares fitting procedure. The collisionally narrowed profile compares more favorable to the observed profiles. Values of the line strengths and self broadening coeffiencients, determined from the least square fitting process, are presented in tabular form. It is found that the experssion by Watson are in closest agreement with the experimentally determined strengths. The self broadening coefficients are compared with the measurements of several other investigators.

Fluoride sensing by catechol-based π-electron systems.

PubMed

An, Byeong-Kwan; Wang, Xin; Burn, Paul L; Meredith, Paul

2010-11-15

We have developed new catechol-based sensors that can detect fluoride via fluorescence or optical absorption even in the presence of other halides. The level and sensitivity of detection of the sensing molecules is dependent on the chromophore length, which is controlled by the number of thiophene units (one to three) within the chromophore. The sensor with three thiophene units, (E)-2-(2,2'-terthiophen-5-yl)-3-(3,4-dihydroxyphenyl)acrylonitrile, gives the best response to fluoride. By using fluorescence measurements fluoride is detectable over the concentration range 1.7 μM to 200 μM. Importantly, when adsorbed onto a solid support the fluorescent catechol dye can be used to detect the presence of fluoride in aqueous solution.

Degradation characteristic of monoazo, diazo and anthraquinone dye by UV / H2O2 process

NASA Astrophysics Data System (ADS)

Abidin, Che Zulzikrami Azner; Fahmi, Muhammad Ridwan; Fazara, Md Ali Umi; Nadhirah, Siti Nurfatin

2014-10-01

In this study, the degradation characteristic of monoazo, diazo and anthraquinone dye by UV / H2O2 process was evaluated based on the trend of color, chemical oxygen demand (COD) and total organic carbon (TOC) removal. Three types of dyes consist of monoazo, diazo and anthraquinone dyes were used to compare the degradation mechanism of the dyes. The UV / H2O2 experiments were conducted in a laboratory scale cylindrical glass reactor operated in semi-batch mode. The UV/Vis characterization of monoazo, diazo and anthraquinone dye indicated that the rapid degradation of the dyes by UV / H2O2 process is meaningful with respect to decolourization, as a result of the azo bonds and substitute antraquinone chromophore degradation. However, this process is not efficient for aromatic amines removal. The monoazo MO was difficult to be decolorized than diazo RR120 dye, which imply that number of sulphonic groups in the dye molecules determines the reactivity with hydroxyl radical. The increased in COD removal is the evidence for oxidation and decreased in carbon content of dye molecules. TOC removal analysis shows that low TOC removal of monoazo MO and diazo RR120, as compared to anthraquinone RB19 may indicate an accumulation of by-products that are resistant to the H2O2 photolysis.

A measurement and modeling study of temperature in living and fixed tissue during and after radiofrequency exposure.

PubMed

Bermingham, Jacqueline F; Chen, Yuen Y; McIntosh, Robert L; Wood, Andrew W

2014-04-01

Fluorescent intensity of the dye Rhodamine-B (Rho-B) decreases with increasing temperature. We show that in fresh rat brain tissue samples in a custom-made radiofrequency (RF) tissue exposure device, temperature rise due to RF radiation as measured by absorbed dye correlates well with temperature measured nearby by fiber optic probes. Estimates of rate of initial temperature rise (using both probe measurement and the dye method) accord well with estimates of local specific energy absorption rate (SAR). We also modeled the temperature characteristics of the exposure device using combined electromagnetic and finite-difference thermal modeling. Although there are some differences in the rate of cooling following cessation of RF exposure, there is reasonable agreement between modeling and both probe measurement and dye estimation of temperature. The dye method also permits measurement of regional temperature rise (due to RF). There is no clear evidence of local differential RF absorption, but further refinement of the method may be needed to fully clarify this issue. © 2014 Wiley Periodicals, Inc.

Design of two-photon molecular tandem architectures for solar cells by ab initio theory† †Electronic supplementary information (ESI) available: Visualizations of molecular orbitals, one-particle mechanisms and a table with Kohn–Sham eigenvalues. See DOI: 10.1039/c4sc03835e

PubMed Central

Garcia-Lastra, Juan M.; De La Torre, Gema; Himpsel, F. J.; Rubio, Angel

2015-01-01

An extensive database of spectroscopic properties of molecules from ab initio calculations is used to design molecular complexes for use in tandem solar cells that convert two photons into a single electron–hole pair, thereby increasing the output voltage while covering a wider spectral range. Three different architectures are considered: the first two involve a complex consisting of two dye molecules with appropriately matched frontier orbitals, connected by a molecular diode. Optimized combinations of dye molecules are determined by taking advantage of our computational database of the structural and energetic properties of several thousand porphyrin dyes. The third design is a molecular analogy of the intermediate band solar cell, and involves a single dye molecule with strong intersystem crossing to ensure a long lifetime of the intermediate state. Based on the calculated energy levels and molecular orbitals, energy diagrams are presented for the individual steps in the operation of such tandem solar cells. We find that theoretical open circuit voltages of up to 1.8 V can be achieved using these tandem designs. Questions about the practical implementation of prototypical devices, such as the synthesis of the tandem molecules and potential loss mechanisms, are addressed. PMID:29142685

Highly efficient volume hologram multiplexing in thick dye-doped jelly-like gelatin.

PubMed

Katarkevich, Vasili M; Rubinov, Anatoli N; Efendiev, Terlan Sh

2014-08-01

Dye-doped jelly-like gelatin is a thick-layer self-developing photosensitive medium that allows single and multiplexed volume phase holograms to be successfully recorded using pulsed laser radiation. In this Letter, we present a method for multiplexed recording of volume holograms in a dye-doped jelly-like gelatin, which provides significant increase in their diffraction efficiency. The method is based on the recovery of the photobleached dye molecule concentration in the hologram recording zone of gel, thanks to molecule diffusion from other unexposed gel areas. As an example, an optical recording of a multiplexed hologram consisting of three superimposed Bragg gratings with mean values of the diffraction efficiency and angular selectivity of ∼75% and ∼21^', respectively, is demonstrated by using the proposed method.

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

Zhou, Xuan; Deeb, Claire; Kostcheev, Sergei

We report a self-developing anisotropic gold/polymer hybrid nanosystem that precisely places dye molecules at the plasmonic hotspot of metal nanostructures for sensing and photonics applications. Unlike conventional molecule-particle configurations, the anisotropic hybrid nanosystem (AHN) introduces an anisotropic spatial distribution of dye-containing active medium. This allows us to precisely overlap the near-field spatial distribution with the active medium and rule out the contribution from the background molecules. This overlap effect selectively highlights the optical response of the molecules of interest, i.e., molecules located at the hotspots. Our AHN consists of gold nanodimers whose gaps have been filled with methylene blue molecules.more » They have been studied by plasmon-enhanced Raman spectroscopy as a probing tool. The AHN opens new doors not only for fundamental studies and photonics applications of molecule-particle interactions, but also for molecular trapping methods at the nanoscale.« less

Measurement of atmospheric OH by titration of near-IR fluorescent dyes

NASA Technical Reports Server (NTRS)

Betterton, Eric A.; Gast, Karl

1994-01-01

Recent research has shown that certain polymethine dyes can be detected at ultratrace levels (greater than or equal to 6x10(exp -14) M) in solution by fluorimetry. These detection limits are possible because of the inherent sensitivity of fluorescence techniques, because the dyes fluoresce in the near infrared region where background interference is negligible, and because powerful infrared diode lasers are now available to improve the signal to noise ratio. Other work has shown that the hydroxyl radical destroys the ability of polymethine dyes to fluoresce. These observations form the basis for a new hydroxyl radical detector that is essentially a fluorometric titrator. Theoretically, the detector should show an acceptable sensitivity and response time. Assuming that the atmospheric HO concentration is about 10(exp -11) moles m(exp -3) (i.e. 10(exp 6) molecules cm(exp -3)), then 10 L of air 'titrated' with 20 mL of 10(exp -11) M dye solution (an easily detected concentration) should result in a drop in the fluorescent signal of 50 percent - a readily detectable change. At a flow rate of 3 L min(exp -1) the sampling time would be 3 minutes. The biggest potential problem is selectivity: other oxidants may also cause the fluorescence signal to be lost. The chemistry of polymethine dyes has not been studied in detail and so no quantitative data are available. However, a survey of the literature suggests that in general HO should react up to six orders of magnitude faster than HO2 and other radicals such as RO2 and RO. It should also react much more rapidly than H2O2 and O3. Thus it may be possible to discriminate kinetically against potential interfering substances. It was shown in the laboratory that 10(exp -4) M H2O2 has little effect on the absorption spectrum of the dye IR125 over a period of hours but that the band at 780 nm is slowly lost in water over a period of days even under argon in the dark. By contrast, DMSO solutions of IR125 are stable.

Synthesis and characterization of organic dyes with various electron-accepting substituents for p-type dye-sensitized solar cells.

PubMed

Weidelener, Martin; Powar, Satvasheel; Kast, Hannelore; Yu, Ze; Boix, Pablo P; Li, Chen; Müllen, Klaus; Geiger, Thomas; Kuster, Simon; Nüesch, Frank; Bach, Udo; Mishra, Amaresh; Bäuerle, Peter

2014-11-01

Four new donor-π-acceptor dyes differing in their acceptor group have been synthesized and employed as model systems to study the influence of the acceptor groups on the photophysical properties and in NiO-based p-type dye-sensitized solar cells. UV/Vis absorption spectra showed a broad range of absorption coverage with maxima between 331 and 653 nm. Redox potentials as well as HOMO and LUMO energies of the dyes were determined from cyclic voltammetry measurements and evaluated concerning their potential use as sensitizers in p-type dye-sensitized solar cells (p-DSCs). Quantum-chemical density functional theory calculations gave further insight into the frontier orbital distributions, which are relevant for the electronic processes in p-DSCs. In p-DSCs using an iodide/triiodide-based electrolyte, the polycyclic 9,10-dicyano-acenaphtho[1,2-b]quinoxaline (DCANQ) acceptor-containing dye gave the highest power conversion efficiency of 0.08%, which is comparable to that obtained with the perylenemonoimide (PMI)-containing dye. Interestingly, devices containing the DCANQ-based dye achieve a higher V(OC) of 163 mV compared to 158 mV for the PMI-containing dye. The result was further confirmed by impedance spectroscopic analysis showing higher recombination resistance and thus a lower recombination rate for devices containing the DCANQ dye than for PMI dye-based devices. However, the use of the strong electron-accepting tricyanofurane (TCF) group played a negative role in the device performance, yielding an efficiency of only 0.01% due to a low-lying LUMO energy level, thus resulting in an insufficient driving force for efficient dye regeneration. The results demonstrate that a careful molecular design with a proper choice of the acceptor unit is essential for development of sensitizers for p-DSCs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synergistic effect of sodium and yeast in improving the efficiency of DSSC sensitized with extract from petals of Kigelia Africana

NASA Astrophysics Data System (ADS)

Shalini, S.; Balasundaraprabhu, R.; Satish Kumar, T.; Sivakumaran, K.; Kannan, M. D.

2018-05-01

TiO2 nanostructures with two different dopants, sodium and yeast have been successfully synthesized by hydrothermal method. Doping sodium is found to extend the absorbance of TiO2 into the visible region as well as it acts as mordant in fixing and improving the absorption of dye. Yeast, as a dopant, can help in absorption of more anthocyanins from the natural dye extract by TiO2 and also aids in retaining the colour of the dye and increases the stability of the dye at varying pH. Anthocyanins are the major class of pigment present in the newly addressed maroon, velvety and trumpet shaped flower "Kigelia Africana". X-ray diffraction analysis revealed the formation of rutile phase for all the samples. Field Emission Scanning Electron microscopy images revealed the formation of nanorods and nanoflowers with change in dopant as well as their concentration. The photoelectric conversion efficiency of DSSC with undoped TiO2 photoelectrode is 0.87% and DSSC with 6% Na doped TiO2 photoelectrode is 1.56%. The efficiency of DSSC with 6% Na+6% yeast doped TiO2 photoelectrode is found to increase from 2.09% (DSSC with 6% Na+4% yeast doped TiO2 photoelectrode) to 2.31% on varying the dopant concentration. Doping is also found to increase the dye absorption and superior charge transport efficiency which in turn helps to improve the performance of DSSC.

Coumarin-indole conjugate donor-acceptor system: Synthesis, photophysical properties, anion sensing ability, theoretical and biological activity studies of two coumarin-indole based push-pull dyes

NASA Astrophysics Data System (ADS)

Aksungur, Tuğçe; Aydıner, Burcu; Seferoğlu, Nurgül; Özkütük, Müjgan; Arslan, Leyla; Reis, Yasemin; Açık, Leyla; Seferoğlu, Zeynel

2017-11-01

Two coumarin-indole conjugate fluorescent dyes having donor-acceptor-donor (D-A-D) (CI-1 and CI-2) were synthesized, and characterized using IR, 1H/13C NMR and HRMS. The absorption and emission properties of the dyes were determined in different solvents. The anion sensitivity and selectivity of the dyes were studied with some anions (CN-, F-, AcO-, Cl-, Br-, I-, HSO4- and H2PO4-) in DMSO, and their interaction mechanisms were evaluated by spectrophotometric and 1H NMR titration techniques. In addition, the molecular and electronic structures of CI-1, as well as the molecular complexes of CI-1, formed with the anions (F- and AcO-), were obtained theoretically and confirmed by DFT and TD-DFT calculations. CI-1 behaves as a colorimetric chemosensor for selective and sensitive detection of CN- in DMSO/H2O (9:1) over other competing anions such as F- and AcO-. However, only CN- interacts with chromophore CI-2 via Michael addition and the main absorption maxima shifts hypsochromically with an observed distinctive color change from orange to yellow. For using as a optic dye, the thermal stability properties of the dyes was determined by TGA (Thermal Gravimetric Analysis). Antimicrobial, antifungal and DNA-ligand interaction studies of the dyes were also examined. The dyes cause conformational changes on DNA and selectively bind to nucleotides of A/A and G/G.

Cosensitization of D-A-π-A quinoxaline organic dye: efficiently filling the absorption valley with high photovoltaic efficiency.

PubMed

Pei, Kai; Wu, Yongzhen; Li, Hui; Geng, Zhiyuan; Tian, He; Zhu, Wei-Hong

2015-03-11

In the efficient cosensitization, the pure organic sensitizers with high molecular extinction coefficients and long wavelength response are highly preferable since the dye loading amount for each dye in cosensitization is decreased with respect to single dye sensitization. A D-A-π-A featured quinoxaline organic sensitizer IQ21 is specifically designed. The high conjugation building block of 4H-cyclopenta[2,1-b:3,4-b']dithiophene (CPDT) is introduced as the π bridge, instead of the traditional thiophene unit, especially in realizing high molecular extinction coefficients (up to 66 600 M(-1) cm(-1)) and extending the light response wavelength. With respect to the reference dye IQ4, the slightly lower efficiency of IQ21 (9.03%) arises from the decrease of VOC, which offsets the gain in JSC. While cosensitized with a smaller D-π-A dye S2, the efficiency in IQ21 is further improved to 10.41% (JSC = 19.8 mA cm(-2), VOC = 731 mV, FF = 0.72). The large improvement in efficiency is attributed to the well-matched molecular structures and loading amounts of both dyes in the cosensitization system. We also demonstrated that coabsorbent dye S2 can distinctly compensate the inherent drawbacks of IQ21, not only enhancing the response intensity of IPCE, making up the absorption defects around low wavelength region of IPCE, but also repressing the charge recombination rate to some extent.

Application of fluorescent dyes for some problems of bioelectromagnetics

NASA Astrophysics Data System (ADS)

Babich, Danylo; Kylsky, Alexandr; Pobiedina, Valentina; Yakunov, Andrey

2016-04-01

Fluorescent organic dyes solutions are used for non-contact measurement of the millimeter wave absorption in liquids simulating biological tissue. There is still not any certain idea of the physical mechanism describing this process despite the widespread technology of microwave radiation in the food industry, biotechnology and medicine. For creating adequate physical model one requires an accurate command of knowledge concerning to the relation between millimeter waves and irradiated object. There were three H-bonded liquids selected as the samples with different coefficients of absorption in the millimeter range like water (strong absorption), glycerol (medium absorption) and ethylene glycol (light absorption). The measurements showed that the greatest response to the action of microwaves occurs for glycerol solutions: R6G (building-up luminescence) and RC (fading luminescence). For aqueous solutions the signal is lower due to lower quantum efficiency of luminescence, and for ethylene glycol — due to the low absorption of microwaves. In the area of exposure a local increase of temperature was estimated. For aqueous solutions of both dyes the maximum temperature increase is about 7° C caused with millimeter waves absorption, which coincides with the direct radio physical measurements and confirmed by theoretical calculations. However, for glycerol solution R6G temperature equivalent for building-up luminescence is around 9° C, and for the solution of ethylene glycol it's about 15°. It is assumed the possibility of non-thermal effect of microwaves on the different processes and substances. The application of this non-contact temperature sensing is a simple and novel method to detect temperature change in small biological objects.

Plasmon enhanced heterogeneous electron transfer with continuous band energy model

NASA Astrophysics Data System (ADS)

Zhao, Dandan; Niu, Lu; Wang, Luxia

2017-08-01

Photoinduced charge injection from a perylene dye molecule into the conduction band of a TiO2 system decorated by a metal nanoparticles (MNP) is studied theoretically. Utilizing the density matrix theory the charge transfer dynamics is analyzed. The continuous behavior of the TiO2 conduction band is accounted for by a Legendre polynomials expansion. The simulations consider optical excitation of the dye molecule coupled to the MNP and the subsequent electron injection into the TiO2 semiconductor. Due to the energy transfer coupling between the molecule and the MNP optical excitation and subsequent charge injection into semiconductor is strongly enhanced. The respective enhancement factor can reach values larger than 103. Effects of pulse duration, coupling strength and energetic resonances are also analyzed. The whole approach offers an efficient way to increase charge injection in dye-sensitized solar cells.

Rose bengal in poly(2-hydroxyethyl methacrylate) thin films: self-quenching by photoactive energy traps

NASA Astrophysics Data System (ADS)

Ezquerra Riega, Sergio D.; Rodríguez, Hernán B.; San Román, Enrique

2017-03-01

The effect of dye concentration on the fluorescence,ΦF, and singlet molecular oxygen,ΦΔ, quantum yields of rose bengal loaded poly(2-hydroxyethyl methacrylate) thin films (∼200 nm thick) was investigated, with the aim of understanding the effect of molecular interactions on the photophysical properties of dyes in crowded constrained environments. Films were characterized by absorption and fluorescence spectroscopy, singlet molecular oxygen (1O2) production was quantified using a chemical monitor, and the triplet decay was determined by laser flash-photolysis. For the monomeric dilute dye, ΦF = 0.05 ± 0.01 and ΦΔ = 0.76 ± 0.14. The effect of humidity and the photostability of the dye were also investigated. Spectral changes in absorption and fluorescence in excess of 0.05 M and concentration self-quenching after 0.01 M are interpreted in the context of a quenching radius model. Calculations of energy migration and trapping rates were performed assuming random distribution of the dye. Best fits of fluorescence quantum yields with concentration are obtained in the whole concentration range with a quenching radius r Q = 1.5 nm, in the order of molecular dimensions. Agreement is obtained only if dimeric traps are considered photoactive, with an observed fluorescence quantum yield ratio ΦF,trap/ΦF,monomer ≈ 0.35. Fluorescent traps are capable of yielding triplet states and 1O2. Results show that the excited state generation efficiency, calculated as the product between the absorption factor and the fluorescence quantum yield, is maximized at around 0.15 M, a very high concentration for random dye distributions. Relevant information for the design of photoactive dyed coatings is provided.

Investigating the effect of various extracting solvents on the potential use of red-apple skin (Malus domestica) as natural sensitizer for dye-sensitized solar cell

NASA Astrophysics Data System (ADS)

Saputro, Aldhi; Mizan, Adlan; Sofyan, Nofrijon; Yuwono, Akhmad Herman

2017-03-01

In the current investigation, the natural dye extracted from red-apple (Malus domestica) skin was used as natural sensitizer for dye sensitized solar cell (DSSC) application. The present study was specifically aimed at observing the effect of different solvents, i.e. deionized water, ethanol, and acidified ethanol, on the performance of the natural dye and thus the DSSC. For synthesis purposes, red-apple skin was peeled off, dried, crushed and furthermore extracted with ratio red-apple skin powder to solvent 1:20 w/v for 2 hours at 50°C under mechanical stirring. Subsequently, the resulting natural dyes with different solvents were examined by Fourier transform infrared (FTIR) to analyze their functional groups, UV-Vis spectroscopy to observe their absorption spectra for a wide range of wavelength, while TiO2 nanoparticle used as the semiconductor oxide layer in the device was characterized by field emission scanning electron microscope (FESEM). The FTIR results showed that the red-apple skin has anthocyanin group which functions as the sensitizer agent for photon energy absorption from the sunlight. The UV-Vis spectroscopy results showed that ethanol solvent has higher absorption of sunlight wavelength as compared to those of deionized water and acidified ethanol solvents. The performance test of the fabricated DSSC showed the prototype made of the red apple skin dye extracted by ethanol solvent can provide the highest open circuit voltage (Voc) up to 324 mV and efficiency around 0.046%. On the basis of investigation, it has been found that ethanol was the best solvent to extract anthocyanin from the red-apple skin.

Quantitative comparison of airborne remote-sensed and in situ Rhodamine WT dye and temperature during RIVET & IB09

NASA Astrophysics Data System (ADS)

Lenain, L.; Clark, D. B.; Guza, R. T.; Hally-Rosendahl, K.; Statom, N.; Feddersen, F.

2012-12-01

The transport and evolution of temperature, sediment, chlorophyll, fluorescent dye, and other tracers is of significant oceanographic interest, particularly in complex coastal environments such as the nearshore, river mouths, and tidal inlets. Remote sensing improves spatial coverage over in situ observations, and ground truthing remote sensed observations is critical for its use. Here, we present remotely sensed observations of Rhodamine WT dye and Sea Surface Temperature (SST) using the SIO Modular Aerial Sensing System (MASS) and compare them with in situ observations from the IB09 (0-300 m seaward of the surfzone, Imperial Beach, CA, October 2009) and RIVET (New River Inlet, NC, May 2012) field experiments. Dye concentrations are estimated from a unique multispectral camera system that measures the emission and absorption wavelengths of Rhodamine WT dye. During RIVET, dye is also characterized using a pushbroom hyperspectral imaging system (SPECIM AISAEagle VNIR 400-990 nm) while SST is estimated using a long-wave infrared camera (FLIR SC6000HS) coupled with an infrared pyrometer (Heitronics KT19.85II). Repeated flight passes over the dye plume were conducted approximately every 5 min for up to 4.5 hr in duration with a swath width ranging from 400 to 2000 m (altitude dependent), and provided a unique spatio-temporal depiction of the plume. A dye proxy is developed using the measured radiance at the emission and absorption wavelengths of the Rhodamine WT dye. During IB09 and RIVET, in situ dye and temperature were measured with two GPS-tracked jet skis, a small boat, and moored observations. The in situ observations are compared with the remotely sensed data in these two complex coastal environments. Funding was provided by the Office of Naval Research.

Optoelectronic and Photovoltaic Performances of Pyridine Based Monomer and Polymer Capped ZnO Dye-Sensitized Solar Cells.

PubMed

Singh, Satbir; Raj, Tilak; Singh, Amarpal; Kaur, Navneet

2016-06-01

The present research work describes the comparative analysis and performance characteristics of 4-pyridine based monomer and polymer capped ZnO dye-sensitized solar cells. The N, N-dimethyl-N4-((pyridine-4yl)methylene) propaneamine (4,monomer) and polyamine-4-pyridyl Schiff base (5, polymer) dyes were synthesized through one step condensation reaction between 4-pyridinecarboxaldehyde 1 and N, N-dimethylpropylamine 2/polyamine 3. Products obtained N, N-dimethyl-N4-((pyridine-4yl)methylene)propaneamine (4) and polyamine-4-pyridyl Schiff base (5) were purified and characterized using 1H, 13C NMR, mass, IR and CHN spectroscopy. Both the dyes 4 and 5 were further coated over ZnO nanoparticles and characterized using SEM, DLS and XRD analysis. Absorption profile and emission profile was monitored using fluorescence and UV-Vis absorption spectroscopy. A thick layer of these inbuilt dye linked ZnO nanoparticles of dyes (4) and (5) was pasted on one of the conductive side of ITO glass followed with a liquid electrolyte and counter electrode of the same conductive glass. Polyamine-4-pyridyl Schiff base polymer (5) decorated dye sensitized solar cell has shown better exciting photovoltaic properties in the form of short circuit current density (J(sc) = 6.3 mA/cm2), open circuit photo voltage (V(oc) = 0.7 V), fill factor (FF = 0.736) than monomer decorated dye sensitized solar cell. Polymer dye (5) based ZnO solar cell has shown a maximum solar power to electrical conversion efficiency of 3.25%, which is enhanced by 2.16% in case of monomer dye based ZnO solar cell under AM 1.5 sun illuminations.

One-step, room temperature, colorimetric melamine sensing using an in-situ formation of silver nanoparticles through modified Tollens process

NASA Astrophysics Data System (ADS)

Wang, Huiying; Chen, Dinglong; Yu, Longquan; Chang, Ming; Ci, Lijie

2015-02-01

We have developed a rapid, sensitive, one-step, and selective colorimetric detection method for melamine (MEL) in milk powder based upon an in-situ formation of silver nanoparticles (AgNPs) through modified Tollens process at room temperature. The triazine ring N atoms of MEL molecule were strategically designed to complex the Ag+ through electron donor-acceptor interaction. During the AgNPs formation procedure, the MEL molecule, which has been covalently bonded with the Ag+ ions, was adsorbed to the surface of as-prepared AgNPs, resulting in the aggregation of the adjacent AgNPs with detectable decreases of absorption signal. The concentration of MEL can be determined with the naked eye or a UV-vis spectrometer at which the yellow-to-brown color change associated with aggregate enhancement takes place. This method enables rapid (less than 30 min) and sensitive (limit of detection, LOD, 10 nM) detection, and it was also able to discriminate MEL from sixteen other milk relevant coexisting compounds. This assay does not utilize organic cosolvents, enzymatic reactions, light-sensitive dye molecules, lengthy protocols, or sophisticated instrumentation thereby overcoming some of the limitations of conventional methods.

Improving the efficiency of water splitting in dye-sensitized solar cells by using a biomimetic electron transfer mediator

PubMed Central

Zhao, Yixin; Swierk, John R.; Megiatto, Jackson D.; Sherman, Benjamin; Youngblood, W. Justin; Qin, Dongdong; Lentz, Deanna M.; Moore, Ana L.; Moore, Thomas A.; Gust, Devens; Mallouk, Thomas E.

2012-01-01

Photoelectrochemical water splitting directly converts solar energy to chemical energy stored in hydrogen, a high energy density fuel. Although water splitting using semiconductor photoelectrodes has been studied for more than 40 years, it has only recently been demonstrated using dye-sensitized electrodes. The quantum yield for water splitting in these dye-based systems has, so far, been very low because the charge recombination reaction is faster than the catalytic four-electron oxidation of water to oxygen. We show here that the quantum yield is more than doubled by incorporating an electron transfer mediator that is mimetic of the tyrosine-histidine mediator in Photosystem II. The mediator molecule is covalently bound to the water oxidation catalyst, a colloidal iridium oxide particle, and is coadsorbed onto a porous titanium dioxide electrode with a Ruthenium polypyridyl sensitizer. As in the natural photosynthetic system, this molecule mediates electron transfer between a relatively slow metal oxide catalyst that oxidizes water on the millisecond timescale and a dye molecule that is oxidized in a fast light-induced electron transfer reaction. The presence of the mediator molecule in the system results in photoelectrochemical water splitting with an internal quantum efficiency of approximately 2.3% using blue light. PMID:22547794

Characterization of the vitreous body of the human eye using a cyanine dye as a spectral and fluorescent probe

NASA Astrophysics Data System (ADS)

Panova, Ina G.; Tatikolov, Alexander S.

2009-02-01

We used one of cyanine dyes as a spectral and fluorescent probe in the study of the composition of the extracellular matrix of the human eye (its vitreous body). Owing to the unique ability of the dye to bind to collagens and human serum albumin, we revealed the simultaneous presence of both types of biomacromolecules in the vitreous body. The formation of the dye complex with human serum albumin leads to appearance of a long-wavelength absorption band (~612 nm) and a steep rise of fluorescence, whereas in the presence of collagens the dye forms J-aggregates with a longer-wavelength absorption band (640-660 nm) and moderate fluorescence. In this work we studied the composition of the human fetus vitreous body and its dynamics from 9 to 31 gestation weeks. On the basis of the data obtained by this method, we may assume that albumin, being a carrier protein, probably provides the vitreous body and surrounding tissues with necessary growth factors, hormones, lipids, vitamins, and some other biomolecules. The data show that the dye is promising not only for study of albumin functions in eye development, but also for characterization of some eye diseases and for analysis of other extracellular media.

Supersensitization of CdS quantum dots with a near-infrared organic dye: toward the design of panchromatic hybrid-sensitized solar cells.

PubMed

Choi, Hyunbong; Nicolaescu, Roxana; Paek, Sanghyun; Ko, Jaejung; Kamat, Prashant V

2011-11-22

The photoresponse of quantum dot solar cells (QDSCs) has been successfully extended to the near-IR (NIR) region by sensitizing nanostructured TiO(2)-CdS films with a squaraine dye (JK-216). CdS nanoparticles anchored on mesoscopic TiO(2) films obtained by successive ionic layer adsorption and reaction (SILAR) exhibit limited absorption below 500 nm with a net power conversion efficiency of ~1% when employed as a photoanode in QDSC. By depositing a thin barrier layer of Al(2)O(3), the TiO(2)-CdS films were further modified with a NIR absorbing squaraine dye. Quantum dot sensitized solar cells supersensitized with a squariand dye (JK-216) showed good stability during illumination with standard global AM 1.5 solar conditions, delivering a maximum overall power conversion efficiency (η) of 3.14%. Transient absorption and pulse radiolysis measurements provide further insight into the excited state interactions of squaraine dye with SiO(2), TiO(2), and TiO(2)/CdS/Al(2)O(3) films and interfacial electron transfer processes. The synergy of combining semiconductor quantum dots and NIR absorbing dye provides new opportunities to harvest photons from different regions of the solar spectrum. © 2011 American Chemical Society

Fabrication, Optimization and Characterization of Natural Dye Sensitized Solar Cell

PubMed Central

Ghann, William; Kang, Hyeonggon; Sheikh, Tajbik; Yadav, Sunil; Chavez-Gil, Tulio; Nesbitt, Fred; Uddin, Jamal

2017-01-01

The dyes extracted from pomegranate and berry fruits were successfully used in the fabrication of natural dye sensitized solar cells (NDSSC). The morphology, porosity, surface roughness, thickness, absorption and emission characteristics of the pomegranate dye sensitized photo-anode were studied using various analytical techniques including FESEM, EDS, TEM, AFM, FTIR, Raman, Fluorescence and Absorption Spectroscopy. Pomegranate dye extract has been shown to contain anthocyanin which is an excellent light harvesting pigment needed for the generation of charge carriers for the production of electricity. The solar cell’s photovoltic performance in terms of efficiency, voltage, and current was tested with a standard illumination of air-mass 1.5 global (AM 1.5 G) having an irradiance of 100 mW/cm2. After optimization of the photo-anode and counter electrode, a photoelectric conversion efficiency (η) of 2%, an open-circuit voltage (Voc) of 0.39 mV, and a short-circuit current density (Isc) of 12.2 mA/cm2 were obtained. Impedance determination showed a relatively low charge-transfer resistance (17.44 Ω) and a long lifetime, signifying a reduction in recombination losses. The relatively enhanced efficiency is attributable in part to the use of a highly concentrated pomegranate dye, graphite counter electrode and TiCl4 treatment of the photo-anode. PMID:28128369

Fabrication, Optimization and Characterization of Natural Dye Sensitized Solar Cell

NASA Astrophysics Data System (ADS)

Ghann, William; Kang, Hyeonggon; Sheikh, Tajbik; Yadav, Sunil; Chavez-Gil, Tulio; Nesbitt, Fred; Uddin, Jamal

2017-01-01

The dyes extracted from pomegranate and berry fruits were successfully used in the fabrication of natural dye sensitized solar cells (NDSSC). The morphology, porosity, surface roughness, thickness, absorption and emission characteristics of the pomegranate dye sensitized photo-anode were studied using various analytical techniques including FESEM, EDS, TEM, AFM, FTIR, Raman, Fluorescence and Absorption Spectroscopy. Pomegranate dye extract has been shown to contain anthocyanin which is an excellent light harvesting pigment needed for the generation of charge carriers for the production of electricity. The solar cell’s photovoltic performance in terms of efficiency, voltage, and current was tested with a standard illumination of air-mass 1.5 global (AM 1.5 G) having an irradiance of 100 mW/cm2. After optimization of the photo-anode and counter electrode, a photoelectric conversion efficiency (η) of 2%, an open-circuit voltage (Voc) of 0.39 mV, and a short-circuit current density (Isc) of 12.2 mA/cm2 were obtained. Impedance determination showed a relatively low charge-transfer resistance (17.44 Ω) and a long lifetime, signifying a reduction in recombination losses. The relatively enhanced efficiency is attributable in part to the use of a highly concentrated pomegranate dye, graphite counter electrode and TiCl4 treatment of the photo-anode.

Dye-binding protein assay using a long-wave-absorbing cyanine probe.

PubMed

Zheng, Hong; Mao, Yu Xia; Li, Dong Hui; Zhu, Chang Qing

2003-07-01

A simple and fast protein assay that involves the binding of water-soluble sulfonate heptamethylene cyanine to protein is described. The binding of the dye to protein causes a shift in the absorption maximum of the dye from 778 to 904 nm, and the increase in absorption at 904 nm is monitored. This assay is very reproducible, of good color stability for at least 80 min, and sensitive at the 100 ng/mL level of human serum albumin (HSA) when a spectrophotometer with near-infrared wavelength is used to measure absorbance. Few chemicals except ionic surfactants such as cetyltrimethylammonium bromide and sodium dodecyl sulfonate interfere with the assay. Purified proteins have different capacities to interact with the dye; under the experimental conditions, the linear ranges of bovine serum albumin (BSA), HSA and gamma-IgG were 200-2000, 100-2400, and 200-3000 ng/mL, respectively. The relative standard deviation for the five replicate determinations of 1200 ng/mL BSA is 2.1%.

Optical limiting properties of 3,5-dipyrenylvinyleneBODIPY dyes at 532 nm

NASA Astrophysics Data System (ADS)

Kubheka, Gugu; Sanusi, Kayode; Mack, John; Nyokong, Tebello

2018-02-01

The optical limiting (OL) properties of 3,5-dipyrenylvinyleneBODIPY dyes that contain both electron withdrawing and donating moieties have been investigated by using the z-scan technique at 532 nm in the nanosecond pulse range. The extension of the π-conjugation at the 3,5-positions with pyrenylvinylene groups results in a ca. 200 nm red shift of the main BODIPY spectral band to ca. 700 nm, so there is relatively weak absorbance at 532 nm under ambient light conditions. Reverse saturable absorbance (RSA) profiles are observed in response to incident pulsed laser light that is consistent with a two photon absorption-assisted excited state absorption (ESA) mechanism in CH2Cl2 solution and when the dyes are embedded in poly(bisphenol carbonate A) (PBC) polymer thin films. This demonstrates that 3,5-divinyleneBODIPY dyes are potentially suitable for use in OL applications, since limiting threshold fluence (Ilim) values of below 0.95 J cm-2 are observed when thin films are prepared.

Structural and quantum chemical analysis of exciton coupling in homo- and heteroaggregate stacks of merocyanines

NASA Astrophysics Data System (ADS)

Bialas, David; Zitzler-Kunkel, André; Kirchner, Eva; Schmidt, David; Würthner, Frank

2016-09-01

Exciton coupling is of fundamental importance and determines functional properties of organic dyes in (opto-)electronic and photovoltaic devices. Here we show that strong exciton coupling is not limited to the situation of equal chromophores as often assumed. Quadruple dye stacks were obtained from two bis(merocyanine) dyes with same or different chromophores, respectively, which dimerize in less-polar solvents resulting in the respective homo- and heteroaggregates. The structures of the quadruple dye stacks were assigned by NMR techniques and unambiguously confirmed by single-crystal X-ray analysis. The heteroaggregate stack formed from the bis(merocyanine) bearing two different chromophores exhibits remarkably different ultraviolet/vis absorption bands compared with those of the homoaggregate of the bis(merocyanine) comprising two identical chromophores. Quantum chemical analysis based on an extension of Kasha's exciton theory appropriately describes the absorption properties of both types of stacks revealing strong exciton coupling also between different chromophores within the heteroaggregate.

Bombyx mori silk: From mechanical properties to functionalities

NASA Astrophysics Data System (ADS)

Koh, Leng Duei

Bombyx mori silkworms are the main producer of silk worldwide. It has been used as high-end textile fibers and as surgical sutures, and is being further developed for various emerging biomedical applications including drug delivery, tissue engineering, sensing, and imaging. The silk fibroin features a hierarchical architecture consisting of beta-sheet crystallites embedded in a less ordered amorphous matrix, which accounts for its unique combination of lustre appearance, soft-to-touch texture, and impressive mechanical properties. Notably, many applications of silk take advantage of its impressive mechanical properties, which by nature surpass many natural and synthetic materials. Interestingly, both the silkworm silk and spider dragline silk share similar hierarchical architecture but possess great disparity in mechanical properties. Inspired by spider dragline silk with much superior strength and toughness, there is an ever growing interest to enhance the mechanical properties of Bombyx mori silk. Here, we design a green and facile feeding method to modulate the structures of silk fibroin at the nanoscale using citric acid (CA), and achieved greatly enhanced mechanical properties. The silk obtained (i.e., CA silk) emerges to be the intrinsically toughest silkworm silk, with mechanical properties that exceed those of the previously reported natural and enhanced silkworm silk, and compare well with those of naturally produced spider silk (including those from spiders Araneus diadematus, Nephila clavipes, etc.).The underlying interactions of CA with fibroin structures are revealed by both advanced characterizations and simulations. It is found that CA interacts with fibroin, resulted in remarkably shorter crystallites, and thus giving the outstanding strength and toughness of the CA silk. The greatly enhanced mechanical properties are expected to lead to better functionalities and wider applications of the Bombyx mori silkworm silk. Silkworms usually produce white silk with normal feed containing no xenobiotics. Here, through introducing fluorescent xenobiotics into silkworm's diet and monitoring the resulting color and fluorescence in the silkworm's body, we established an understanding on the in vivo uptake of xenobiotics in silkworms that leads to direct production of intrinsically colored and/or luminescent silk by the silkworms. The molecular properties-directed absorption, distribution and excretion of xenobiotics were investigated using a series of fluorescent molecules as model compounds in a silkworm model. The efficient uptake of xenobiotics into silk is further studied through quantitative analysis of the intrinsically colored and highly luminescent silk secreted by silkworm. Criteria for effective uptake have been established based on the relationship between the structure-dependent hydrophobicity of various dyes vs. the amount selectively absorbed into the silk. The biological incorporation of dyes into silk, in particular its fibroin is a greener method of producing the functional silk because it eliminates the need of an external dyeing process, along with the resources (water, energy and additional chemicals) associated with conventional dyeing of silk. Beyond the absorption of dyes to produce color and luminescence in the silk, this feeding concept can also be expanded to incorporate other functional molecules (e.g., drugs, antibacterial agents, perfumes and nutrients) into silk with therapeutic or nutritional value.

DNA origami based Au-Ag-core-shell nanoparticle dimers with single-molecule SERS sensitivity

NASA Astrophysics Data System (ADS)

Prinz, J.; Heck, C.; Ellerik, L.; Merk, V.; Bald, I.

2016-03-01

DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled.DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled. Electronic supplementary information (ESI) available: Additional information about materials and methods, designs of DNA origami templates, height profiles, additional SERS spectra, assignment of DNA bands, SEM images, additional AFM images, FDTD simulations, additional reference spectra for Cy3 and detailed description of EF estimation, simulated absorption and scattering spectra. See DOI: 10.1039/c5nr08674d

Degradation characteristic of monoazo, diazo and anthraquinone dye by UV/H{sub 2}O{sub 2} process

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

Abidin, Che Zulzikrami Azner, E-mail: zulzikrami@unimap.edu.my, E-mail: drfahmi@unimap.edu.my, E-mail: umifazara@unimap.edu.my, E-mail: fatinnadhirah89@gmail.com; Fahmi, Muhammad Ridwan, E-mail: zulzikrami@unimap.edu.my, E-mail: drfahmi@unimap.edu.my, E-mail: umifazara@unimap.edu.my, E-mail: fatinnadhirah89@gmail.com; Fazara, Md Ali Umi, E-mail: zulzikrami@unimap.edu.my, E-mail: drfahmi@unimap.edu.my, E-mail: umifazara@unimap.edu.my, E-mail: fatinnadhirah89@gmail.com

2014-10-24

In this study, the degradation characteristic of monoazo, diazo and anthraquinone dye by UV/H{sub 2}O{sub 2} process was evaluated based on the trend of color, chemical oxygen demand (COD) and total organic carbon (TOC) removal. Three types of dyes consist of monoazo, diazo and anthraquinone dyes were used to compare the degradation mechanism of the dyes. The UV/H{sub 2}O{sub 2} experiments were conducted in a laboratory scale cylindrical glass reactor operated in semi-batch mode. The UV/Vis characterization of monoazo, diazo and anthraquinone dye indicated that the rapid degradation of the dyes by UV/H{sub 2}O{sub 2} process is meaningful with respectmore » to decolourization, as a result of the azo bonds and substitute antraquinone chromophore degradation. However, this process is not efficient for aromatic amines removal. The monoazo MO was difficult to be decolorized than diazo RR120 dye, which imply that number of sulphonic groups in the dye molecules determines the reactivity with hydroxyl radical. The increased in COD removal is the evidence for oxidation and decreased in carbon content of dye molecules. TOC removal analysis shows that low TOC removal of monoazo MO and diazo RR120, as compared to anthraquinone RB19 may indicate an accumulation of by-products that are resistant to the H{sub 2}O{sub 2} photolysis.« less

Effects of Pulsed Electromagnetic Fields on Breast Cancer Cell Line MCF 7 Using Absorption Spectroscopy.

PubMed

Alcantara, Dominic Z; Soliman, Ian Jerry S; Pobre, Romeric F; Naguib, Raouf N G

2017-07-01

We present an analysis of the effects of pulsed electromagnetic fields (PEMF) with 3.3 MHz carrier frequency and modulated by audio resonant frequencies on the MCF-7 breast cancer cell line in vitro using absorption spectroscopy. This involves a fluorescence dye called PrestoBlue™ Cell Viability Reagent and a spectrophotometry to test the viability of MCF-7 breast cancer cells under different PEMF treatment conditions in terms of the cell absorption values. The DNA molecule of the MCF-7 breast cancer cells has an electric dipole property that renders it sensitive and reactive to applied electromagnetic fields. Resonant frequencies derived from four genes mutated in MCF-7 breast cancer cells [rapamycin-insensitive companion of mammalian target of rapamycin (RICTOR), peroxisome proliferator-activated receptor (PPARG), Nijmegen breakage syndrome 1 (NBN) and checkpoint kinase 2 (CHEK2)] were applied in generating square pulsed electromagnetic waves. Effects were monitored through measurement of absorption of the samples with PrestoBlue™, and the significance of the treatment was determined using the t-test. There was a significant effect on MCF-7 cells after treatment with PEMF at the resonant frequencies of the following genes for specific durations of exposure: RICTOR for 10 min, PPARG for 10 min, NBN for 15 min, and CHEK2 for 5 min. Copyright© 2017, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

A small-molecule dye for NIR-II imaging

NASA Astrophysics Data System (ADS)

Antaris, Alexander L.; Chen, Hao; Cheng, Kai; Sun, Yao; Hong, Guosong; Qu, Chunrong; Diao, Shuo; Deng, Zixin; Hu, Xianming; Zhang, Bo; Zhang, Xiaodong; Yaghi, Omar K.; Alamparambil, Zita R.; Hong, Xuechuan; Cheng, Zhen; Dai, Hongjie

2016-02-01

Fluorescent imaging of biological systems in the second near-infrared window (NIR-II) can probe tissue at centimetre depths and achieve micrometre-scale resolution at depths of millimetres. Unfortunately, all current NIR-II fluorophores are excreted slowly and are largely retained within the reticuloendothelial system, making clinical translation nearly impossible. Here, we report a rapidly excreted NIR-II fluorophore (~90% excreted through the kidneys within 24 h) based on a synthetic 970-Da organic molecule (CH1055). The fluorophore outperformed indocyanine green (ICG)--a clinically approved NIR-I dye--in resolving mouse lymphatic vasculature and sentinel lymphatic mapping near a tumour. High levels of uptake of PEGylated-CH1055 dye were observed in brain tumours in mice, suggesting that the dye was detected at a depth of ~4 mm. The CH1055 dye also allowed targeted molecular imaging of tumours in vivo when conjugated with anti-EGFR Affibody. Moreover, a superior tumour-to-background signal ratio allowed precise image-guided tumour-removal surgery.

Nanospectroscopy of thiacyanine dye molecules adsorbed on silver nanoparticle clusters

NASA Astrophysics Data System (ADS)

Ralević, Uroš; Isić, Goran; Anicijević, Dragana Vasić; Laban, Bojana; Bogdanović, Una; Lazović, Vladimir M.; Vodnik, Vesna; Gajić, Radoš

2018-03-01

The adsorption of thiacyanine dye molecules on citrate-stabilized silver nanoparticle clusters drop-cast onto freshly cleaved mica or highly oriented pyrolytic graphite surfaces is examined using colocalized surface-enhanced Raman spectroscopy and atomic force microscopy. The incidence of dye Raman signatures in photoluminescence hotspots identified around nanoparticle clusters is considered for both citrate- and borate-capped silver nanoparticles and found to be substantially lower in the former case, suggesting that the citrate anions impede the efficient dye adsorption. Rigorous numerical simulations of light scattering on random nanoparticle clusters are used for estimating the electromagnetic enhancement and elucidating the hotspot formation mechanism. The majority of the enhanced Raman signal, estimated to be more than 90%, is found to originate from the nanogaps between adjacent nanoparticles in the cluster, regardless of the cluster size and geometry.

Monodisperse Magneto-Fluorescent Bifunctional Nanoprobes for Bioapplications

NASA Astrophysics Data System (ADS)

Zhang, Hongwang; Huang, Heng; Pralle, Arnd; Zeng, Hao

2013-03-01

We present the work on the synthesis of dye-doped monodisperse Fe/SiO2 core/shell nanoparticles as bifunctional probes for bioapplications. Magnetic nanoparticles (NP) have been widely studied as nano-probes for bio-imaging, sensing as well as for cancer therapy. Among all the NPs, Fe NPs have been the focus because they have very high magnetization. However, Fe NPs are usually not stable in ambient due to the fast surface oxidation of the NPs. On the other hand, dye molecules have long been used as probes for bio-imaging. But they are sensitive to environmental conditions. It requires passivation for both so that they can be stable for applications. In this work, monodisperse Fe NPs with sizes ranging from 13-20 nm have been synthesized through the chemical thermal-decomposition in a solution. Silica shells were then coated on the Fe NPs by a two-phase oil-in-water method. Dye molecules were first bonded to a silica precursor and then encapsulated into the silica shell during the coating process. The silica shells protect both the Fe NPs and dye molecules, which makes them as robust probes. The dye doped Fe/SiO2 core/shell NPs remain both highly magnetic and highly fluorescent. The stable dye doped Fe/SiO2NPs have been used as a dual functional probe for both magnetic heating and local nanoscale temperature sending, and their performance will be reported. Research supported by NSF DMR 0547036, DMR1104994.

Sensitization of photoconductivity in ferrocene-containing oligomer by squarylium and merocyanine dyes

NASA Astrophysics Data System (ADS)

Davidenko, N. A.; Ishchenko, A. A.; Kozinets, A. V.; Kostenko, L. I.; Kurdyukova, I. V.; Mokrinskaya, E. V.; Studzinskii, S. L.; Chuprina, N. G.

2011-03-01

We have studied the photoconducting properties of films of ferrocene-containing oligomer with additives of squarylium and merocyanine dyes based on ferrocene and tetranitrofluorene in the dye absorption region. We have studied the characteristic features of the effect of an external magnetic field on the photocurrents. After the magnetic field is turned on, the photocurrent increases in the samples with squarylium dye and decreases in the samples with merocyanine dye. We discuss the hypothesis that in the first case, as a result of an internal photoelectric effect, predominantly triplet charge pairs are formed, while in the second case predominantly singlet charge pairs are formed. The latter may be one of the reasons for the higher photoconductivity of films with squarylium dye compared with merocyanine dye.

Trap formation and energy transfer in pheophorbide a-DAB-dendrimers and pyropheophorbide a-fullerene C 60 hexaadduct molecular systems

NASA Astrophysics Data System (ADS)

Röder, Beate; Ermilov, Eugeny A.; Hackbarth, Steffen; Helmreich, Matthias; Jux, Norbert

2006-04-01

The photophysical properties of DAB-dendrimers from 1 st to 4 th generation as well as Diaminohexane - all substituted with the in maximum achievable quantity of pheophorbide a (Pheo) molecules were studied in comparison with a novel hexapyropheophorbide a - fullerene hexaadduct (FHP6) and a fullerene [6:0]-hexaadduct which carries twelve pyropheophorbide a units (FHP12) using both steady-state and time-resolved spectroscopic methods. It was found that neighboring dye molecules covalently linked to one DAB- or fullerene moiety due to the length and high flexibility of carbon chains could stack with each other. This structural property is the reason for the possibility of formation different types of energy traps, which were resolved experimentally. The dipole-dipole resonance Förster energy transfer between the dye molecules coupled to one complex caused a very fast and efficient delivery of the excitation to a trap. As result the fluorescence as well as the singlet oxygen quantum yields of the different complexes were reduced with increasing number of dye molecules per complex. Nevertheless in every case the singlet oxygen generation was less influenced then the fluorescence quantum yield, exposing the complex to a non-negligible amount of excited oxygen in the singlet state. While the fullerene complexes turned out to be stable under these conditions, the DAB-dendrimer-backbones were completely fragmented to small rudiments carrying just one or a small number of dye molecules.

Four-color single-molecule fluorescence with noncovalent dye labeling to monitor dynamic multimolecular complexes.

PubMed

DeRocco, Vanessa; Anderson, Trevor; Piehler, Jacob; Erie, Dorothy A; Weninger, Keith

2010-11-01

To enable studies of conformational changes within multimolecular complexes, we present a simultaneous, four-color single molecule fluorescence methodology implemented with total internal reflection illumination and camera-based, wide-field detection. We further demonstrate labeling histidine-tagged proteins noncovalently with Tris-nitrilotriacetic acid (Tris-NTA)-conjugated dyes to achieve single molecule detection. We combine these methods to colocalize the mismatch repair protein MutSα on DNA while monitoring MutSα-induced DNA bending using Förster resonance energy transfer (FRET) and to monitor assembly of membrane-tethered SNARE protein complexes.

Four-color single molecule fluorescence with noncovalent dye labeling to monitor dynamic multimolecular complexes

PubMed Central

DeRocco, Vanessa C.; Anderson, Trevor; Piehler, Jacob; Erie, Dorothy A.; Weninger, Keith

2010-01-01

To allow studies of conformational changes within multi-molecular complexes, we present a simultaneous, 4-color single molecule fluorescence methodology implemented with total internal reflection illumination and camera based, wide-field detection. We further demonstrate labeling histidine-tagged proteins non-covalently with tris-Nitrilotriacetic acid (tris-NTA) conjugated dyes to achieve single molecule detection. We combine these methods to co-localize the mismatch repair protein MutSα on DNA while monitoring MutSα-induced DNA bending using Förster resonance energy transfer (FRET) and to monitor assembly of membrane-tethered SNARE protein complexes. PMID:21091445

Single-Molecule Probing of Adsorption and Diffusion on Silica Surfaces

NASA Astrophysics Data System (ADS)

Wirth, Mary J.; Legg, Michael A.

2007-05-01

Single-molecule spectroscopy has emerged as a valuable tool in probing kinetics and dynamic equilibria in adsorption because advances in instrumentation and technology have enabled researchers to obtain high signal-to-noise ratios for common dyes at room temperature. Single-molecule spectroscopy was applied to the study of an important problem in chromatography: peak broadening and asymmetry in the chromatograms of pharmaceuticals, peptides, and proteins. Using DiI, a cationic dye that exhibits the same problematic chromatographic behavior, investigators showed that the adsorption sites that cause chromatographic problems are located at defects on the silica crystal surface.

Influence of chlorine atoms in bay positions of perylene-tetracarboxylic acids on their spectral properties in Langmuir-Blodgett films

NASA Astrophysics Data System (ADS)

Piosik, Emilia; Synak, Anna; Martyński, Tomasz

2018-01-01

The influence of chlorine atoms in the bay positions of the perylene-3,4,9,10-tetracarboxylic acids with the different alkyl chains length on their spectral properties in monomolecular films has been studied. The chlorinated (PCln) and for comparison non-chlorinated (Pn) perylene derivatives were deposited onto quartz plates using a Langmuir-Blodgett (LB) technique. The absorption spectra showed that the PCln and Pn dyes form in monolayers the I- and J-type aggregates, respectively. In turn, their steady-state and time-resolved emission spectra revealed presence of two emitter types, which we assigned to monomers and excimers. The luminescence lifetimes of the PCln monomers and excimers determined with a time-correlated single photon counting method (TCSPC) are significantly shorter than these obtained for the same emitter types in the Pn monolayers. In the case of the chlorinated dyes, the contribution of the monomer emission dominates over the excimer emission and is almost independent from the alkyl chain length. By contrast, the share of the Pn monomer emission increases strongly with a number of carbon atoms in their hydrocarbon chains. The luminescence quantum yields (LQY) of the Pn and PCln monolayers measured in an integrating sphere are in the range of 0.06-0.11. The presented results reveal that the PCln dyes exhibit lower tendency for aggregation than the non-chlorinated derivatives. It can be explained by limited intermolecular interaction between neighbouring PCln molecules caused by deformation of the perylene core as a result of strongly electronegative chlorine atoms in the bay positions of these dyes. Moreover, the strong influence of the alkyl chain length on the Pn aggregation contrary to the case of the PCln derivatives was observed.

Distinguishing between Protein Dynamics and Dye Photophysics in Single-Molecule FRET Experiments

PubMed Central

Chung, Hoi Sung; Louis, John M.; Eaton, William A.

2010-01-01

Abstract Förster resonance energy transfer (FRET) efficiency distributions in single-molecule experiments contain both structural and dynamical information. Extraction of this information from these distributions requires a careful analysis of contributions from dye photophysics. To investigate how mechanisms other than FRET affect the distributions obtained by counting donor and acceptor photons, we have measured single-molecule fluorescence trajectories of a small α/β protein, i.e., protein GB1, undergoing two-state, folding/unfolding transitions. Alexa 488 donor and Alexa 594 acceptor dyes were attached to cysteines at positions 10 and 57 to yield two isomers—donor10/acceptor57 and donor57/acceptor10—which could not be separated in the purification. The protein was immobilized via binding of a histidine tag added to a linker sequence at the N-terminus to cupric ions embedded in a polyethylene-glycol–coated glass surface. The distribution of FRET efficiencies assembled from the trajectories is complex with widths for the individual peaks in large excess of that caused by shot noise. Most of this complexity can be explained by two interfering photophysical effects—a photoinduced red shift of the donor dye and differences in the quantum yield of the acceptor dye for the two isomers resulting from differences in quenching rate by the cupric ion. Measurements of steady-state polarization, calculation of the donor-acceptor cross-correlation function from photon trajectories, and comparison of the single molecule and ensemble kinetics all indicate that conformational distributions and dynamics do not contribute to the complexity. PMID:20159166

Distinguishing between protein dynamics and dye photophysics in single-molecule FRET experiments.

PubMed

Chung, Hoi Sung; Louis, John M; Eaton, William A

2010-02-17

Förster resonance energy transfer (FRET) efficiency distributions in single-molecule experiments contain both structural and dynamical information. Extraction of this information from these distributions requires a careful analysis of contributions from dye photophysics. To investigate how mechanisms other than FRET affect the distributions obtained by counting donor and acceptor photons, we have measured single-molecule fluorescence trajectories of a small alpha/beta protein, i.e., protein GB1, undergoing two-state, folding/unfolding transitions. Alexa 488 donor and Alexa 594 acceptor dyes were attached to cysteines at positions 10 and 57 to yield two isomers-donor(10)/acceptor(57) and donor(57)/acceptor(10)-which could not be separated in the purification. The protein was immobilized via binding of a histidine tag added to a linker sequence at the N-terminus to cupric ions embedded in a polyethylene-glycol-coated glass surface. The distribution of FRET efficiencies assembled from the trajectories is complex with widths for the individual peaks in large excess of that caused by shot noise. Most of this complexity can be explained by two interfering photophysical effects-a photoinduced red shift of the donor dye and differences in the quantum yield of the acceptor dye for the two isomers resulting from differences in quenching rate by the cupric ion. Measurements of steady-state polarization, calculation of the donor-acceptor cross-correlation function from photon trajectories, and comparison of the single molecule and ensemble kinetics all indicate that conformational distributions and dynamics do not contribute to the complexity. Copyright 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Effect of methyl substituents on the electronic transitions in simple meso-aniline-BODIPY based dyes: RI-CC2 and TD-CAM-B3LYP computational investigation

NASA Astrophysics Data System (ADS)

Petrushenko, Igor K.; Petrushenko, Konstantin B.

2018-02-01

The S0 → Si, i = 1-5 electronic transitions of four 8-(4-aniline)-BODIPY and four 8-(N,N-dimethyl)-BODIPY dyes, differ by number and position of methyl substituents in the BODIPY frame, were investigated theoretically using ab initio the coupled cluster doubles (CC2) and TD-CAM-B3LYP methods. Methyl substituents in the BODIPY frame and the aniline fragment at the meso position disturb energy of local excitations S0 → S1, S0 → S3, and S0 → S4 weakly in comparison with the fully unsubstituted BODIPY molecule. These transitions in experimental spectra form the most long-wave absorption bands at ca. 500 nm as well as absorption bands in the region of 300-400 nm. At the same time, the presence of aniline fragments leads to the appearance of new S0 → S2 transitions of the charge transfer character in electronic spectra of BODIPYs. We also found a linear relationship between vertical energy of these charge transfer transitions and the electron donating power of an aniline fragment and electron accepting power of the BODIPY core depending on the number and position of methyl groups. The CC2 method provides the best overall description of the excitation energies in line with the experimental observations. On average, the quality of TD-CAM-B3LYP is almost equal to that of CC2, however the TD method with the CAM-B3LYP functional slightly underestimates the CT excitation energy.

Design of near-infrared dyes for nonlinear optics: toward optical limiting applications at telecommunication wavelengths

NASA Astrophysics Data System (ADS)

Bellier, Quentin; Bouit, Pierre-Antoine; Kamada, Kenji; Feneyrou, Patrick; Malmström, E.; Maury, Olivier; Andraud, Chantal

2009-09-01

The rapid development of frequency-tunable pulsed lasers up to telecommunication wavelengths (1400-1600 nm) led to the design of new materials for nonlinear absorption in this spectral range. In this context, two families of near infra-red (NIR) chromophores, namely heptamethine cyanine and aza-borondipyrromethene (aza-bodipy) dyes were studied. In both cases, they show significant two-photon absorption (TPA) cross-sections in the 1400-1600 nm spectral range and display good optical power limiting (OPL) properties. OPL curves were interpreted on the basis of TPA followed by excited state absorption (ESA) phenomena. Finally these systems have several relevant properties like nonlinear absorption properties, gram scale synthesis and high solubility. In addition, they could be functionalized on several sites which open the way to numerous practical applications in biology, solid-state optical limiting and signal processing.

Photophysical properties of a laser dye (LD-473) in different solvents

NASA Astrophysics Data System (ADS)

Ibnaouf, K. H.; Alhathlool, R.; Ali, M. K. M.

2018-06-01

In this paper, we investigated the spectroscopic properties the 1, 2, 3, 8-tetrahydrofuran, 2, 3, 8-(LD-473) dissolved in seven types of solvents with different concentrations. The absorption, emission, fluorescence and its quantum yield and Stokes shift of LD-473 were measured. The amplified spontaneous emission (ASE) spectra of LD-473 have been obtained using a transverse laser cavity configuration, where the LD-473 was pumped by laser pulses from the third harmonic of an Nd: YAG laser (355 nm). LD-473 in non-polar solvents exhibits dual ASEs around 445 and 470 nm, whereas the corresponding fluorescence spectrum shows only one peak around 437 nm. The peak at 470 nm is due to the combination of two excited molecules and the solvent between them.

Effects of chirp on two-dimensional Fourier transform electronic spectra.

PubMed

Tekavec, Patrick F; Myers, Jeffrey A; Lewis, Kristin L M; Fuller, Franklin D; Ogilvie, Jennifer P

2010-05-24

We examine the effect that pulse chirp has on the shape of two- dimensional electronic spectra through calculations and experiments. For the calculations we use a model two electronic level system with a solvent interaction represented by a simple Gaussian correlation function and compare the resulting spectra to experiments carried out on an organic dye molecule (Rhodamine 800). Both calculations and experiments show that distortions due to chirp are most significant when the pulses used in the experiment have different amounts of chirp, introducing peak shape asymmetry that could be interpreted as spectrally dependent relaxation. When all pulses have similar chirp the distortions are reduced but still affect the anti-diagonal symmetry of the peak shapes and introduce negative features that could be interpreted as excited state absorption.

Near-infrared voltage-sensitive fluorescent dyes optimized for optical mapping in blood-perfused myocardium.

PubMed

Matiukas, Arvydas; Mitrea, Bogdan G; Qin, Maochun; Pertsov, Arkady M; Shvedko, Alexander G; Warren, Mark D; Zaitsev, Alexey V; Wuskell, Joseph P; Wei, Mei-de; Watras, James; Loew, Leslie M

2007-11-01

Styryl voltage-sensitive dyes (e.g., di-4-ANEPPS) have been used successfully for optical mapping in cardiac cells and tissues. However, their utility for probing electrical activity deep inside the myocardial wall and in blood-perfused myocardium has been limited because of light scattering and high absorption by endogenous chromophores and hemoglobin at blue-green excitation wavelengths. The purpose of this study was to characterize two new styryl dyes--di-4-ANBDQPQ (JPW-6003) and di-4-ANBDQBS (JPW-6033)--optimized for blood-perfused tissue and intramural optical mapping. Voltage-dependent spectra were recorded in a model lipid bilayer. Optical mapping experiments were conducted in four species (mouse, rat, guinea pig, and pig). Hearts were Langendorff perfused using Tyrode's solution and blood (pig). Dyes were loaded via bolus injection into perfusate. Transillumination experiments were conducted in isolated coronary-perfused pig right ventricular wall preparations. The optimal excitation wavelength in cardiac tissues (650 nm) was >70 nm beyond the absorption maximum of hemoglobin. Voltage sensitivity of both dyes was approximately 10% to 20%. Signal decay half-life due to dye internalization was 80 to 210 minutes, which is 5 to 7 times slower than for di-4-ANEPPS. In transillumination mode, DeltaF/F was as high as 20%. In blood-perfused tissues, DeltaF/F reached 5.5% (1.8 times higher than for di-4-ANEPPS). We have synthesized and characterized two new near-infrared dyes with excitation/emission wavelengths shifted >100 nm to the red. They provide both high voltage sensitivity and 5 to 7 times slower internalization rate compared to conventional dyes. The dyes are optimized for deeper tissue probing and optical mapping of blood-perfused tissue, but they also can be used for conventional applications.

Effects of nano anatase-rutile TiO2 volume fraction with natural dye containing anthocyanin on the dye sensitized solar cell performance

NASA Astrophysics Data System (ADS)

Agustini, S.; Wahyuono, R. A.; Sawitri, D.; Risanti, D. D.

2013-09-01

Since its first development, efforts to improve efficiency of Dye Sensitized Solar Cell (DSSC) are continuously carried out, either through selection of dye materials, the type of semiconductor, counter electrode design or the sandwiched structure. It is widely known that anatase and rutile are phases of TiO2 that often being used for fabrication of DSSC. Rutile is thermodynamically more stable phase having band-gap suitable for absorption of sunlight spectrum. On the other hand, anatase has higher electrical conductivity, capability to adsorp dye as well as higher electron diffusion coefficient than those of rutile. Present research uses mangosteen pericarp and Rhoeo spathacea extracted in ethanol as natural dye containing anthocyanin. These dyes were characterized by using UV-Vis and FTIR, showing that the absorption maxima peaks obtained at 389 nm and 413 nm, for mangosteen and Rhoeo spathacea, respectively. The nano TiO2 was prepared by means of co-precipitation method. The particle size were 9-11 nm and 54.5 nm for anatase and rutile, respectively, according to Scherrer's equation. DSSCs were fabricated in various volume fractions of anatase and rutile TiO2. The fabricated DSSCs were tested under 17 mW/cm2 of solar irradiation. The current-voltage (I-V) characteristic of DSSCs employing 75%: 25% volume fraction of anatase and rutile TiO2 have outstanding result than others. The highest conversion efficiencies of 0.037% and 0.013% are obtained for DSSC employing natural dye extract from mangosteen pericarp and Rhoeo spathacea, respectively.

Kiss-and-Run Is a Significant Contributor to Synaptic Exocytosis and Endocytosis in Photoreceptors

PubMed Central

Wen, Xiangyi; Saltzgaber, Grant W.; Thoreson, Wallace B.

2017-01-01

Accompanying sustained release in darkness, rod and cone photoreceptors exhibit rapid endocytosis of synaptic vesicles. Membrane capacitance measurements indicated that rapid endocytosis retrieves at least 70% of the exocytotic membrane increase. One mechanism for rapid endocytosis is kiss-and-run fusion where vesicles briefly contact the plasma membrane through a small fusion pore. Release can also occur by full-collapse in which vesicles merge completely with the plasma membrane. We assessed relative contributions of full-collapse and kiss-and-run in salamander photoreceptors using optical techniques to measure endocytosis and exocytosis of large vs. small dye molecules. Incubation with small dyes (SR101, 1 nm; 3-kDa dextran-conjugated Texas Red, 2.3 nm) loaded rod and cone synaptic terminals much more readily than larger dyes (10-kDa Texas Red, 4.6 nm; 10-kDa pHrodo, 4.6 nm; 70-kDa Texas Red, 12 nm) consistent with significant uptake through 2.3–4.6 nm fusion pores. By using total internal reflection fluorescence microscopy (TIRFM) to image individual vesicles, when rods were incubated simultaneously with Texas Red and AlexaFluor-488 dyes conjugated to either 3-kDa or 10-kDa dextran, more vesicles loaded small molecules than large molecules. Using TIRFM to detect release by the disappearance of dye-loaded vesicles, we found that SR101 and 3-kDa Texas Red were released from individual vesicles more readily than 10-kDa and 70-kDa Texas Red. Although 10-kDa pHrodo was endocytosed poorly like other large dyes, the fraction of release events was similar to SR101 and 3-kDa Texas Red. We hypothesize that while 10-kDa pHrodo may not exit through a fusion pore, release of intravesicular protons can promote detection of fusion events by rapidly quenching fluorescence of this pH-sensitive dye. Assuming that large molecules can only be released by full-collapse whereas small molecules can be released by both modes, our results indicate that 50%–70% of release from rods involves kiss-and-run with 2.3–4.6 nm fusion pores. Rapid retrieval of vesicles by kiss-and-run may limit membrane disruption of release site function during ongoing release at photoreceptor ribbon synapses. PMID:28979188

Superior Adsorption and Regenerable Dye Adsorbent Based on Flower-Like Molybdenum Disulfide Nanostructure

NASA Astrophysics Data System (ADS)

Han, Sancan; Liu, Kerui; Hu, Linfeng; Teng, Feng; Yu, Pingping; Zhu, Yufang

2017-03-01

Herein we report superior dye-adsorption performance for flower-like nanostructure composed of two dimensional (2D) MoS2 nanosheets by a facile hydrothermal method, more prominent adsorption of cationic dye compared with anodic dye indicates the dye adsorption performance strongly depends on surface charge of MoS2 nanosheets. The adsorption mechanism of dye is analyzed, the kinetic data of dye adsorption fit well with the pseudo-second-order model, meanwhile adsorption capability at different equilibrium concentrations follows Langmuir model, indicating the favorability and feasibility of dye adsorption. The regenerable property for MoS2 with full adsorption of dye molecules by using alkaline solution were demonstrated, showing the feasibility of reuse for the MoS2, which is promising in its practical water treatment application.

Evidence for excited state intramolecular charge transfer in benzazole-based pseudo-stilbenes.

PubMed

Santos, Fabiano da Silveira; Descalzo, Rodrigo Roceti; Gonçalves, Paulo Fernando Bruno; Benvenutti, Edilson Valmir; Rodembusch, Fabiano Severo

2012-08-21

Two azo compounds were obtained through the diazotization reaction of aminobenzazole derivatives and N,N-dimethylaniline using clay montmorillonite KSF as catalyst. The synthesized dyes were characterized using elemental analysis, Fourier transform infrared spectroscopy, and (13)C and (1)H NMR spectroscopy in solution. Their photophysical behavior was studied using UV-vis and steady-state fluorescence in solution. These dyes present intense absorption in the blue region. The spectral features of the azo compounds can be related to the pseudo-stilbene type as well as the E isomer of the dyes. Excitation at the absorption maxima does not produce emissive species in the excited state. However, excitation around 350 nm allowed dual emission of fluorescence, from both a locally excited (LE, short wavelength) and an intramolecular charge transfer (ICT, long wavelength) state, which was corroborated by a linear relation of the fluorescence maximum (ν(max)) versus the solvent polarity function (Δf) from the Lippert-Mataga correlation. Evidence of TICT in these dyes was discussed from the viscosity dependence of the fluorescence intensity in the ICT emission band. Theoretical calculations were also performed in order to study the geometry and charge distribution of the dyes in their ground and excited electronic states. Using DFT methods at the theoretical levels BLYP/Aug-cc-pVDZ, for geometry optimizations and frequency calculations, and B3LYP/6-311+G(2d), for single-point energy evaluations, the calculations revealed that the least energetic and most intense photon absorption leads to a very polar excited state that relaxes non-radioactively, which can be associated with photochemical isomerization.

Near-Infrared Emitting Squaraine Dyes with High 2PA Cross Sections for Multiphoton Fluorescence Imaging

PubMed Central

Ahn, Hyo-Yang; Yao, Sheng; Wang, Xuhua; Belfield, Kevin D.

2012-01-01

Designed to achieve high two-photon absorptivity, new near infrared (NIR) emitting squaraine dyes, (E)-2-(1-(2-(2-methoxyethoxy)ethyl)-5-(3,4,5-trimethoxystyryl)-1H-pyrrol-2-yl)-4-(1-(2-(2-methoxyethoxy)ethyl)-5-(3,4,5-trimethoxystyryl)-2H-pyrrolium-2-ylidene)-3-oxocyclobut-1-enolate (1) and (Z)-2-(4-(dibutylamino)-2-hydroxyphenyl)-4-(4-(dibutyliminio)-2-hydroxycyclohexa-2,5-dienylidene)-3-oxocyclobut-1-enolate (2) were synthesized and characterized. Their linear photophysical properties were investigated via UV-visible absorption spectroscopy and fluorescence spectroscopy in various solvents, while their nonlinear photophysical properties were investigated using a combination of two-photon induced fluorescence and open aperture z-scan methods. Squaraine 1 exhibited a high two-photon absorption (2PA) cross section (δ2PA), ~ 20,000 GM at 800 nm, and high photostability with the photochemical decomposition quantum yield one order of magnitude lower than Cy 5, a commercially available pentamethine cyanine NIR dye. The cytotoxicity of the squaraine dyes were evaluated in HCT 116 and COS 7 cell lines to assess the potential of these probes for biomedical imaging. The viability of both cell lines was maintained above 80% at dye concentrations up to 30 μM, indicating good biocompatibility of the probes. Finally, one-photon fluorescence microscopy (1PFM) and two-photon fluorescence microscopy (2PFM) imaging was accomplished after incubation of micelle-encapsulated squaraine probes with HCT 116 and COS 7 cells, demonstrating their potential in 2PFM bioimaging. PMID:22591003

Investigation of excited-state relaxation processes of organic dyes by time-resolved spectroscopy

NASA Astrophysics Data System (ADS)

Przhonska, O.; Slominsky, Yu.; Kachkovsky, A.; Stahl, U.; Senoner, M.; Dähne, S.

1996-04-01

The results of the measurements of the fluorescence decay kinetics of the new series of polymethine dyes in liquid and solid polymeric media are reported. The effects of polymeric media on absorption-relaxation-emission processes are studied at wide excitation, emission and temperature regions.

Measurement of Scattering and Absorption Cross Sections of Dyed Microspheres

PubMed Central

Gaigalas, Adolfas K; Choquette, Steven; Zhang, Yu-Zhong

2013-01-01

Measurements of absorbance and fluorescence emission were carried out on aqueous suspensions of polystyrene (PS) microspheres with a diameter of 2.5 µm using a spectrophotometer with an integrating sphere detector. The apparatus and the principles of measurements were described in our earlier publications. Microspheres with and without green BODIPY@ dye were measured. Placing the suspension inside an integrating sphere (IS) detector of the spectrophotometer yielded (after a correction for fluorescence emission) the absorbance (called A in the text) due to absorption by BODIPY@ dye inside the microsphere. An estimate of the absorbance due to scattering alone was obtained by subtracting the corrected BODIPY@ dye absorbance (A) from the measured absorbance of a suspension placed outside the IS detector (called A1 in the text). The absorption of the BODIPY@ dye inside the microsphere was analyzed using an imaginary index of refraction parameterized with three Gaussian-Lorentz functions. The Kramer-Kronig relation was used to estimate the contribution of the BODIPY@ dye to the real part of the microsphere index of refraction. The complex index of refraction, obtained from the analysis of A, was used to analyze the absorbance due to scattering ((A1- A) in the text). In practice, the analysis of the scattering absorbance, A1-A, and the absorbance, A, was carried out in an iterative manner. It was assumed that A depended primarily on the imaginary part of the microsphere index of refraction with the other parameters playing a secondary role. Therefore A was first analyzed using values of the other parameters obtained from a fit to the absorbance due to scattering, A1-A, with the imaginary part neglected. The imaginary part obtained from the analysis of A was then used to reanalyze A1-A, and obtain better estimates of the other parameters. After a few iterations, consistent estimates were obtained of the scattering and absorption cross sections in the wavelength region 300 nm to 800 nm. PMID:26401422

Engendering Long-Term Air and Light Stability of a TiO2-Supported Porphyrinic Dye via Atomic Layer Deposition.

PubMed

Hoffeditz, William L; Son, Ho-Jin; Pellin, Michael J; Farha, Omar K; Hupp, Joseph T

2016-12-21

Organic and porphyrin-based chromophores are prevalent in liquid-junction photovoltaic and photocatalytic solar-cell chemistry; however, their long-term air and light instability may limit their practicality in real world technologies. Here, we describe the protection of a zinc porphyrin dye, adsorbed on nanoparticulate TiO 2 , from air and light degradation by a protective coating of alumina grown with a previously developed post-treatment atomic layer deposition (ALD) technique. The protective Al 2 O 3 ALD layer is deposited using dimethylaluminum isopropoxide as an Al source; in contrast to the ubiquitous ALD precursor trimethylaluminum, dimethylaluminum isopropoxide does not degrade the zinc porphyrin dye, as confirmed by UV-vis measurements. The growth of this protective ALD layer around the dye can be monitored by an in-reactor quartz crystal microbalance (QCM). Furthermore, greater than 80% of porphyrin light absorption is retained over ∼1 month of exposure to air and light when the protective coating is present, whereas almost complete loss of porphyrin absorption is observed in less than 2 days in the absence of the ALD protective layer. Applying the Al 2 O 3 post-treatment technique to the TiO 2 -adsorbed dye allows the dye to remain in electronic contact with both the semiconductor surface and a surrounding electrolyte solution, the combination of which makes this technique promising for numerous other electrochemical photovoltaic and photocatalytic applications, especially those involving the dye-sensitized evolution of oxygen.

Exciplex formation in blended spin-cast films of fluorene-linked dyes and bisphthalimide quenchers.

PubMed

Stewart, David J; Dalton, Matthew J; Swiger, Rachel N; Cooper, Thomas M; Haley, Joy E; Tan, Loon-Seng

2013-05-16

Spin-cast films of dyes (donor-π-donor, donor-π-acceptor, and acceptor-π-acceptor type, where the donor is Ph2N-, the acceptor is 2-benzothiazoyl, and the π-linker is 9,9-diethylfluorene) blended with nonconjugated bisphthalimides were prepared. Upon visible-light excitation of the dyes, quenching of the excited state occurs by exciplex formation between dye and bisphthalimide molecules or, in some cases, by excimer formation or aggregation-induced emission between two dye molecules. The extent of exciplex formation is dependent on the driving force, which can be calculated using the energy difference between the lowest unoccupied molecular orbitals (LUMOs) of the dyes and bisphthalimides. The results show that complete exciplex formation occurs when this driving force is greater than 0.57 eV whereas partial exciplex formation occurs when the driving force is between 0.28 and 0.57 eV. The exciplex emission energies can also be predicted by calculating the difference between the LUMO level of the bisphthalimide and the highest occupied molecular orbital (HOMO) of the dye. These calculated values, which were obtained from the electrochemically determined energy levels, showed good agreement with the observed emission energies. The exciplex lifetimes were found to be significantly longer than the lifetimes of the lone dyes. These exciplexes formed from nonlinked donors and acceptors in the solid state might have potential uses in nonlinear photonics.

Effects of alkyl spacer group length on Vis-NIR absorption behavior in FTC-like guest-host EO polymers

NASA Astrophysics Data System (ADS)

Barto, Richard R., Jr.; Bedworth, Peter V.; Epstein, Joseph A.; Ermer, Susan P.; Taylor, Rebecca E.; Frank, Curtis W.

2003-07-01

Spectral absorption behavior of a series of FTC-like dyes of varying shape incorporated into amorphous polycarbonate (APC) is characterized by photothermal deflection spectroscopy. Previous Monte Carlo calculations by Dalton and Robinson predict a strong dependence of the macroscopic nonlinear optical susceptibility on the chromophore waist:length aspect ratio in electric field-poled films. This dependence arises from London interactions between chromophores, which are expected to influence the absorption characteristics of the composite both by changing the local polarity of the medium and through dipole interactions. It is expected that these interactions will play a role in the absorption characteristics of unpoled films as well. Of particular interest are the spectral characteristics of the red edge of the main dye electronic absorption peak, and the fine structure in the near-IR, dominated by overtones of fundamental C-H stretching and bending modes. The spectral structure in these key regions can be influenced by inter- and intramolecular interactions and conformational changes in the dye. The near-IR structure, in turn, will dictate absorption loss in optical devices prepared from these materials at key transmission wavelengths (1.3 and 1.55 um). In this study, a homologous series of spacer lengths, ranging from ethyl to hexyl, attached to an FTC-like NLO chromophore, LMCO-46M, is characterized by a combination of photothermal deflection spectroscopy (PDS) and UV-Vis spectroscopy to examine the effects of the molecular environment on near-IR loss at 1090 nm, 1300 nm and 1550 nm.

Design of Far-Red Sensitizing Squaraine Dyes Aiming Towards the Fine Tuning of Dye Molecular Structure.

PubMed

Morimoto, Takuya; Fujikawa, Naotaka; Ogomi, Yuhei; Pandey, Shyam S; Ma, Tingli; Hayase, Shuzi

2016-04-01

Model squaraine dyes having sharp and narrow absorptions mainly in the far-red wavelength region has been logically designed, synthesized and used for their application as sensitizer in the dyesensitized solar cells (DSSC). In order to have fine control on energetics, dyes having same mother core and alkyl chain length varying only in molecular symmetry and position of substituent were designed. It has been found that even keeping all other structural factor constant, only positional variation of substituent leads to not only in the variation of energetics by 0.1 eV but affects the photovoltaic characteristics also. Optimum concentration of dye de-aggregating agent was found to be 100 times with respect to the sensitizing dye concentration. Amongst dyes utilized in this work best performance was obtained for unsymmetrical dye SQ-40 giving a photoconversion efficiency of 4.01% under simulated solar irradiation at global AM 1.5.

New fluorescent symmetrically substituted perylene-3,4,9,10-dianhydride-azohybrid dyes: Synthesis and spectroscopic studies

NASA Astrophysics Data System (ADS)

Saeed, Aamer; Shabir, Ghulam

2014-12-01

Five phenolic azo-dyes (3a-e) were synthesized by diazo coupling of the suitably substituted anilines (1a-e) with phenol at low temperature in alkaline medium. The resulting dyes have low solubility in aqueous medium due to lack of carboxylic or sulfonic solubilizing functionalities. The hybridization of perylene dianhydride with phenolic azo-dyes was achieved by the nucleophilic aromatic substitution (SNAr) reaction of perylene-3,4,9,10-dianhydride 4 with phenolic azo-dyes 3a-e in basic medium. The hybrid dyes exhibit absorption maxima λmax in the range 440-460 nm in aqueous medium due to presence of azo linkage and highly conjugated system of π bonds. Fluorescence spectra of these dyes in water show sharp emission peaks with small band widths. The structures of perylene-azo dyes were confirmed by FTIR and NMR spectroscopy.

Some heterocyclic azo dyes derived from thiazolyl derivatives; synthesis; substituent effects and solvatochromic studies

NASA Astrophysics Data System (ADS)

Yazdanbakhsh, M. R.; Mohammadi, A.; Abbasnia, M.

2010-12-01

A series of azo disperse dyes were synthesized by coupling reaction of N, N-diethylaniline, 2-anilinoethanol and N-phenyl-2,2'-iminodiethanol with diazotized aminothiazolyl derivatives as diazo components. These dyes have been prepared in good yields, and were characterized by UV-Vis, FT-IR and 1H NMR spectroscopic techniques. The effects of solvent polarity and various pH on dyes in the visible absorption spectra were evaluated. All dyes exhibit an excellent correlation coefficient ( r > 0.92) for the linear solvation energy relationship with π* values calculated by Kamlet et al. The influence of the pH on the dyes with electron-donating group implied that these dyes exist in acid-base equilibrium in acidic environment. The effect of substituents of both coupler and diazo component on the color of dyes was investigated as well.

Tunable lasers for water vapor measurements and other lidar applications

NASA Technical Reports Server (NTRS)

Gammon, R. W.; Mcilrath, T. J.; Wilkerson, T. D.

1977-01-01

A tunable dye laser suitable for differential absorption (DIAL) measurements of water vapor in the troposphere was constructed. A multi-pass absorption cell for calibration was also constructed for use in atmospheric DIAL measurements of water vapor.

Ultrafast Spectroscopic Studies of Two-Photon States in Third Order Optical Processes of Dye Chromophores.

NASA Astrophysics Data System (ADS)

Yu, Yi-Zhong

1995-01-01

Conjugated organic and polymeric materials usually have large, nonresonant third order optical nonlinearity due to correlations of their delocalized pi -electrons. Most materials studied so far show positive values of third order nonlinear susceptibility when all frequencies that generate the third order effect are below any optical transition. A new class of organic molecules, namely indole squarylium (ISQ) and anilinium squarylium (BSQ), exhibit negative < gamma(-omega_4;omega_1, omega_2,omega_3)> when all three frequencies, omega_1, omega_2 and omega_3, lie below the first electronic transition. Although quantum many-electron calculations based on multiple-excitation configuration interaction have shown that the negative third order coefficient is essentially due to the contribution from high-lying two-photon states, the field of experimental studies exploring the microscopic origins of the negative squaraines remains uncultivated. The work presented in this thesis involves extensive experimental investigation of squaraines using techniques such as time-resolved transit absorption spectroscopy and saturable absorption. Theoretical simulations studying nonlinear absorption behavior of a simplified two-level system with ultrashort pulses are also presented. Part of the thesis is dedicated to the development, fabrication and characterization of our ultrafast laser system which offers tunable femtosecond pulses at wavelengths from UV to IR and served as a major tool in the experimental measurements. The dynamics of the population inversion between the ground state and the first excited state was also investigated through time-resolved experiments. The experiment results agree well with the theoretical predictions. Strong couplings between the gateway state and high-lying two-photon states were observed in BSQ squarylium molecules, which suggested a complete quantum calculation with multiple energy levels is required to correctly describe the negative third order effect.

Synthesis of phthalocyanine doped sol-gel materials

NASA Technical Reports Server (NTRS)

Dunn, Bruce

1993-01-01

The synthesis of sol-gel silica materials doped with three different types of metallophthalocyanines has been studied. Homogeneous materials of good optical quality were prepared and the first optical limiting measurements of dyes in sol-gel hosts were carried out. The properties of these solid state limiters are similar to limiters based on phthalocyanine (Pc) in solution. Sol-gel silica materials containing copper, tin and germanium phthalocyanines were investigated. The initial step in all cases was to prepare silica sols by the sonogel method using tetramethoxy silane (TMOS), HCl and distilled water. Thereafter, the synthesis depended upon the specific Pc and its solubility characteristics. Copper phthalocyanine tetrasulfonic acid tetra sodium salt (CuPc4S) is soluble in water and various doping levels (1 x 10 (exp -4) M to 1 x 10 (exp -5) M) were added to the sol. The group IV Pc's, SnPc(OSi(n-hexyl)3)2 and GePc(OSi(n-hexyl)3)2, are insoluble in water and the process was changed accordingly. In these cases, the compounds were dissolved in THF and then added to the sol. The Pc concentration in the sol was 2 x 10(exp -5)M. The samples were then aged and dried in the standard method of making xerogel monoliths. Comparative nanosecond optical limiting experiments were performed on silica xerogels that were doped with the different metallophthalocyanines. The ratio of the net excited state absorption cross section (sigma(sub e)) to the ground state cross section (sigma(sub g)) is an important figure of merit that is used to characterize these materials. By this standard the SnPc sample exhibits the best limiting for the Pc doped sol-gel materials. Its cross section ratio of 19 compares favorably with the value of 22 that was measured in toluene. The GePc materials appear to not be as useful as those containing SnPc. The GePc doped solids exhibit a higher onset energy (2.5 mj and lower cross section ratio, 7. The CuPc4S sol-gel material has a still lower cross section ratio, 4, however, the tetrasulfonate groups make the dye soluble in water which greatly facilitates its incorporation into the sol-gel matrix. The nonlinear transmission of CuPc4S in a pH 2 buffer solution and in a silica xerogel were compared. It is evident that the CuPc4S preserves its optical limiting behavior in the sol-gel matrix, indicating that the fundamental excited state absorption process is essentially the same for a molecule in solution or in the solid state. Although the spectroscopic details of energy level lifetimes are unknown, the significance is that passive optical limiting has been achieved in the solid state via incorporation of a dye into an inorganic host. The only compromise occurs at the extremely high energy regime where photobleaching is observed. This is a result of the limited mobility of the dye molecules in the solid silica host relative to a liquid host. The effects of photodegradation in the xerogel are additive, whereas the solution provides a supply of fresh molecules that are free to enter the active volume between pulses.

An ensemble and single-molecule fluorescence microscopy investigation of phase-separated monolayer films stained with Nile Red.

PubMed

Lu, Yin; Porterfield, Robyn; Thunder, Terri; Paige, Matthew F

2011-01-01

Phase-separated Langmuir-Blodgett monolayer films prepared from mixtures of arachidic acid (C19H39COOH) and perfluorotetradecanoic acid (C13F27COOH) were stained via spin-casting with the polarity sensitive phenoxazine dye Nile Red, and characterized using a combination of ensemble and single-molecule fluorescence microscopy measurements. Ensemble fluorescence microscopy and spectromicroscopy showed that Nile Red preferentially associated with the hydrogenated domains of the phase-separated films, and was strongly fluorescent in these areas of the film. These measurements, in conjunction with single-molecule fluorescence imaging experiments, also indicated that a small sub-population of dye molecules localizes on the perfluorinated regions of the sample, but that this sub-population is spectroscopically indistinguishable from that associated with the hydrogenated domains. The relative importance of selective dye adsorption and local polarity sensitivity of Nile Red for staining applications in phase-separated LB films as well as in cellular environments is discussed in context of the experimental results. Copyright © 2010 Elsevier B.V. All rights reserved.

Warm-White-Light-Emitting Diode Based on a Dye-Loaded Metal-Organic Framework for Fast White-Light Communication.

PubMed

Wang, Zhiye; Wang, Zi; Lin, Bangjiang; Hu, XueFu; Wei, YunFeng; Zhang, Cankun; An, Bing; Wang, Cheng; Lin, Wenbin

2017-10-11

A dye@metal-organic framework (MOF) hybrid was used as a fluorophore in a white-light-emitting diode (WLED) for fast visible-light communication (VLC). The white light was generated from a combination of blue emission of the 9,10-dibenzoate anthracene (DBA) linkers and yellow emission of the encapsulated Rhodamine B molecules. The MOF structure not only prevents dye molecules from aggregation-induced quenching but also efficiently transfers energy to the dye for dual emission. This light-emitting material shows emission lifetimes of 1.8 and 5.3 ns for the blue and yellow components, respectively, which are significantly shorter than the 200 ns lifetime of Y 3 Al 5 O 12 :Ce 3+ in commercial WLEDs. The MOF-WLED device exhibited a modulating frequency of 3.6 MHz for VLC, six times that of commercial WLEDs.

The use of ionic salt dyes as amorphous, thermally stable emitting layers in organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Chondroudis, Konstantinos; Mitzi, David B.

2000-01-01

The conversion of two neutral dye molecules (D) to ionic salts (H2N-D-NH2ṡ2HX) and their utilization as emitting layers in organic light-emitting diodes (OLEDs) is described. The dye salts, AEQTṡ2HCl and APTṡ2HCl, can be deposited as amorphous films using conventional evaporation techniques. X-ray diffraction and scanning electron microscopy analysis, coupled with thermal annealing studies, demonstrate the resistance of the films to crystallization. This stability is attributed to strong ionic forces between the relatively rigid molecules. OLEDs incorporating such salts for emitting layers exhibit better thermal stability compared with devices made from the corresponding neutral dyes (H2N-D-NH2). These results suggest that ionic salts may more generally enable the formation of thermally stable, amorphous emitting, and charge transporting layers.

Pyronin Y (basic xanthene dye)-bentonite composite: A spectroscopic study

NASA Astrophysics Data System (ADS)

Tabak, A.; Kaya, M.; Yilmaz, N.; Meral, K.; Onganer, Y.; Caglar, B.; Sungur, O.

2014-02-01

The expansion by 1.43 Angstrom of basal spacing and the shift to higher frequencies of in-plane ring vibrations of the Pyronin Y molecule at 1603 and 1527 cm-1 on the formation of Pyronin Y-bentonite composite exhibited that the dye cations might be oriented as a monolayer form in the interlamellar spacing with aromatic rings parallel to clay layers. Thermal analysis results of this composite compared to those of raw bentonite signified the different outer sphere water entities associated with the replacement of inorganic cations with organic dye cations and the gradual decomposition of the organic molecule in the interlamellar spacing. Thermo-Infrared spectra of Pyronin Y-bentonite sample up to high temperatures showed the thermal stability of the dye-clay composite as a result of the presence of π interactions. The pore structure characteristics of Pyronin Y-bentonite composite exhibited the increase in the number of mesopores during formation of the composite.

Improving the Performance of Gold-Nanoparticle-Doped Solid-State Dye Laser Using Thermal Conversion Effect

NASA Astrophysics Data System (ADS)

An, N. T. M.; Lien, N. T. H.; Hoang, N. D.; Hoa, D. Q.

2018-04-01

Energy transfer between spherical gold nanoparticles with size of more than 15 nm and molecules of organic dye 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4 H-pyran (DCM) has been studied. Such radiative energy transfer led to high local temperature, giving rise to a bleaching effect that resulted in rapid degradation of the laser medium. Gold nanoparticles were dispersed at concentrations from 5 × 109 particles/mL to 5 × 1010 particles/mL in DCM polymethylmethacrylate polymer using a radical polymerization process with 2,2'-azobis(isobutyronitrile) (AIBN) as initiator. Using the fast thermoelectric cooling method, the laser medium stability was significantly improved. The output stability of a distributed feedback dye laser pumped by second-harmonic generation from a neodymium-doped yttrium aluminum garnet (Nd:YAG) laser was investigated. Moreover, bidirectional energy transfer between gold nanoparticles and dye molecules was observed.

Enhanced photothermal lens using a photonic crystal surface

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

Zhao, Yunfei; Liu, Longju; Zhao, Xiangwei

2016-08-15

A photonic crystal (PC)-enhanced photothermal lens (PTL) is demonstrated for the detection of optically thin light absorption materials. The PC-enhanced PTL system is based on a pump-probe scheme consisting of a PC surface, pump laser beam, and probe laser beam. Heated by the pump beam, light absorption materials on the PC surface generate the PTL and cause a substantial change to the guided-mode resonance supported by the PC structure. The change of the PC resonance is detected using the probe laser beam by measuring its reflectivity from the PC surface. When applied to analyze dye molecules deposited on the PCmore » substrate, the developed system is capable of enhancing the PTL signal by 10-fold and reducing the lowest distinguishable concentration by 8-fold, in comparison to measuring without utilizing the PC resonance. The PC-enhanced PTL was also used to detect gold nanoparticles on the PC surface and exhibited a 20-fold improvement of the lowest distinguishable concentration. The PC-enhanced PTL technology offers a potential tool to obtain the absorption signatures of thin films in a broad spectral range with high sensitivity and inexpensive instrumentation. As a result, this technology will enable a broad range of applications of photothermal spectroscopy in chemical analysis and biomolecule sensing.« less

Probing the Relative Photoinjection Yields of Monomer and Aggregated Dyes into ZnO Crystals.

PubMed

King, Laurie A; Parkinson, B A

2017-01-17

Cyanine dyes, often used in dye-sensitized solar cells (DSSCs), form a range of molecular species from monomers to large H and J aggregates in both solution and when adsorbed at a photoelectrode surface. To determine the relative capability of the different dye species to inject photoexcited electrons into a wideband gap oxide semiconductor, sensitization at a single-crystal zinc oxide surface was studied by simultaneous attenuated reflection (ATR) ultraviolet-visible (UV-vis) absorption and photocurrent spectroscopy measurements. ATR measurements enable identification of the dye species populating the surface with simultaneous photocurrent spectroscopy to identify the contribution of the various dye forms to photocurrent signal. We study the dye 2,2'-carboxymethylthiodicarbocyanine bromide that is particularly prone to aggregation both in solution and at the surface of sensitized oxide semiconductors.

Masked red-emitting carbopyronine dyes with photosensitive 2-diazo-1-indanone caging group.

PubMed

Kolmakov, Kirill; Wurm, Christian; Sednev, Maksim V; Bossi, Mariano L; Belov, Vladimir N; Hell, Stefan W

2012-03-01

Caged near-IR emitting fluorescent dyes are in high demand in optical microscopy but up to now were unavailable. We discovered that the combination of a carbopyronine dye core and a photosensitive 2-diazo-1-indanone residue leads to masked near-IR emitting fluorescent dyes. Illumination of these caged dyes with either UV or visible light (λ < 420 nm) efficiently generates fluorescent compounds with absorption and emission at 635 nm and 660 nm, respectively. A high-yielding synthetic route with attractive possibilities for further dye design is described in detail. Good photostability, high contrast, and a large fluorescence quantum yield after uncaging are the most important features of the new compounds for non-invasive imaging in high-resolution optical microscopy. For use in immunolabelling the caged dyes were decorated with a (hydrophilic) linker and an (activated) carboxyl group.

Metal-free organic dyes for dye-sensitized solar cells: from structure: property relationships to design rules.

PubMed

Mishra, Amaresh; Fischer, Markus K R; Bäuerle, Peter

2009-01-01

Dye-sensitized solar cells (DSSC) have attracted considerable attention in recent years as they offer the possibility of low-cost conversion of photovoltaic energy. This Review focuses on recent advances in molecular design and technological aspects of metal-free organic dyes for applications in dye-sensitized solar cells. Special attention has been paid to the design principles of these dyes and on the effect of various electrolyte systems. Cosensitization, an emerging technique to extend the absorption range, is also discussed as a way to improve the performance of the device. In addition, we report on inverted dyes for photocathodes, which constitutes a relatively new approach for the production of tandem cells. Special consideration has been paid to the correlation between the molecular structure and physical properties to their performance in DSSCs.

Photoelectric characterization of fabricated dye-sensitized solar cell using dye extracted from red Siahkooti fruit as natural sensitizer

NASA Astrophysics Data System (ADS)

Mozaffari, Sayed Ahmad; Saeidi, Mahsa; Rahmanian, Reza

2015-05-01

Natural dye extracted from Siahkooti fruit with/without purification by solid phase extraction (SPE) technique was used in the fabrication of DSSC as natural sensitizer. The UV-Vis absorption spectroscopy and Fourier transform infrared (FTIR) were employed to indicate the presence of anthocyanins in the fruit of red Siahkooti. The photoelectrochemical performance and the efficiency of assembled DSSC using Siahkooti fruit dye extract were evaluated and efficiency enhancement was obtained by a preliminary purification of extracted dye. The efficiency and fill factor of the DSSC using purified Siahkooti fruit dye were 0.32% and 0.73%, respectively. The results successfully showed that the DSSC, using Siahkooti fruit extract as a dye sensitizer, is useful for the preparation of environmentally friendly, low-cost, renewable and clean sources of energy.

Challenges in designing a Taqman-based multiplex assay for the simultaneous detection of Herpes simplex virus types 1 and 2 and Varicella-zoster virus.

PubMed

Weidmann, Manfred; Armbruster, Katrin; Hufert, Frank T

2008-08-01

To optimise molecular detection of herpesviruses an internally controlled multiplex Taqman-PCR for the detection of Herpes simplex virus 1 (HSV1), Herpes simplex virus 2 (HSV2) and Varicella-zoster virus (VZV) was developed. The selection of the dye combination working on the ABI 7700 cycler for this multiplex PCR revealed crosstalk phenomena between several combinations of reference dyes and reporter dyes. A final dye combination with CY5 as reference dye and FAM/JOE/TXR as reporter dyes was selected. The influence of the concentration of the internal positive control (IPC) concentration on the quantitative results of HSV1, HSV2 and VZV positive patient samples was analysed. The results indicate that high IPC concentrations are detrimental for the sensitivity of the multiplex assay and that the presence of the IPC molecule narrows the dynamic range of the duplex PCRs between any of the virus PCRs and the IPC-PCR. The optimised multiplex assay detecting HSV1, HSV2 and VZV using 10(3) IPC molecules showed a performance and sensitivity comparable to that of the individual assays.

Spectroscopic and thermal properties of short wavelength metal (II) complexes containing α-isoxazolylazo-β-diketones as co-ligands

NASA Astrophysics Data System (ADS)

Huang, Fuxin; Wu, Yiqun; Gu, Donghong; Gan, Fuxi

2005-10-01

Two new azo dyes of α-isoxazolylazo-β-diketones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni 2+ and Cu 2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from the solution forms and from the solid forms. The action of sodium methoxide (NaOMe) on azo dyes in solutions converts hydrazoketo form into azoenol form, so azo dyes are coordinated with metal (II) ions as co-ligands in the azoenol forms. The solubility of all the compounds in common organic solvents such as 2,2,3,3-tetrafluoro-1-propanol (TFP) or chloroform (CHCl 3) and absorption properties of spin-coating thin films were measured. The difference of absorption maxima from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. It is found that these new metal (II) complexes had potential application for high-density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra in blue-violet light region and high thermal stability.

In vitro isolation of small-molecule-binding aptamers with intrinsic dye-displacement functionality

PubMed Central

Yu, Haixiang; Yang, Weijuan; Alkhamis, Obtin; Canoura, Juan; Yang, Kyung-Ae; Xiao, Yi

2018-01-01

Abstract Aptamer-based sensors offer a powerful tool for molecular detection, but the practical implementation of these biosensors is hindered by costly and laborious sequence engineering and chemical modification procedures. We report a simple strategy for directly isolating signal-reporting aptamers in vitro through systematic evolution of ligands by exponential enrichment (SELEX) that transduce binding events into a detectable change of absorbance via target-induced displacement of a small-molecule dye. We first demonstrate that diethylthiatricarbocyanine (Cy7) can stack into DNA three-way junctions (TWJs) in a sequence-independent fashion, greatly altering the dye's absorbance spectrum. We then design a TWJ-containing structured library and isolate an aptamer against 3,4-methylenedioxypyrovalerone (MDPV), a synthetic cathinone that is an emerging drug of abuse. This aptamer intrinsically binds Cy7 within its TWJ domain, but MDPV efficiently displaces the dye, resulting in a change in absorbance within seconds. This assay is label-free, and detects nanomolar concentrations of MDPV. It also recognizes other synthetic cathinones, offering the potential to detect newly-emerging designer drugs, but does not detect structurally-similar non-cathinone compounds or common cutting agents. Moreover, we demonstrate that the Cy7-displacement colorimetric assay is more sensitive than a conventional strand-displacement fluorescence assay. We believe our strategy offers an effective generalized approach for the development of sensitive dye-displacement colorimetric assays for other small-molecule targets. PMID:29361056

Fabrication and characterization of dye-sensitized solar cells based on natural plants

NASA Astrophysics Data System (ADS)

Gu, Peng; Yang, Dingyu; Zhu, Xinghua; Sun, Hui; Li, Jitao

2018-02-01

In this paper, the dye-sensitized solar cells (DSSCs) were fabricated based on natural dyes extracting from carrot, mulberry, purple cabbage, potato, and grapes. The ultraviolet-visible spectra suggested purple cabbage and mulberry possess better absorption at 300-550 nm. The solar cells using purple cabbage as dye achieved a conversion efficiency of 0.162% with short-circuit photocurrent density (Jsc) of 0.621 mA/cm2, open circuit voltage (Voc) of 0.541 V and fill factor (FF) of 0.484. The Infrared spectra revealed the bond of Osbnd H, Csbnd C, Csbnd O, Csbnd H were existed in purple cabbage. Finally, the optimal extraction time of dyes is also presented.

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.

Experimental elaboration and analysis of dye-sensitized TiO2 solar cells (DSSC) dyed by natural dyes and conductive polymers

NASA Astrophysics Data System (ADS)

KałuŻyński, P.; Maciak, E.; Herzog, T.; Wójcik, M.

2016-09-01

In this paper we propose low cost and easy in development fully working dye-sensitized solar cell module made with use of a different sensitizing dyes (various anthocyanins and P3HT) for increasing the absorption spectrum, transparent conducting substrates (vaccum spattered chromium and gold), nanometer sized TiO2 film, iodide and methyl viologen dichloride based electrolyte, and a counter electrode (vaccum spattered platinum or carbon). Moreover, some of the different technologies and optimization manufacturing processes were elaborated for energy efficiency increase and were presented in this paper.

Molecular specificity in photoacoustic microscopy by time-resolved transient absorption.

PubMed

Shelton, Ryan L; Mattison, Scott P; Applegate, Brian E

2014-06-01

We have recently harnessed transient absorption, a resonant two-photon process, for ultrahigh resolution photoacoustic microscopy, achieving nearly an order of magnitude improvement in axial resolution. The axial resolution is optically constrained due to the two-photon process unlike traditional photoacoustic microscopy where the axial resolution is inversely proportional to the frequency bandwidth of the detector. As a resonant process, the arrival time of the two photons need not be instantaneous. Systematically recording the signal as a function of the delay between two pulses will result in the measurement of an exponential decay whose time constant is related to the molecular dynamics. This time constant, analogous to the fluorescence lifetime, but encompassing nonradiative decay as well, can be used to differentiate between molecular systems with overlapping absorption spectra. This is frequently the situation for closely related yet distinct molecules such as redox pairs. In order to enable the measure of the exponential decay, we have reconfigured our transient absorption ultrasonic microscopy (TAUM) system to incorporate two laser sources with precisely controlled pulse trains. The system was tested by measuring Rhodamine 6G, an efficient laser dye where the molecular dynamics are dominated by the fluorescence pathway. As expected, the measured exponential time constant or ground state recovery time, 3.3±0.7  ns, was similar to the well-known fluorescence lifetime, 4.11±0.05  ns. Oxy- and deoxy-hemoglobin are the quintessential pair whose relative concentration is related to the local blood oxygen saturation. We have measured the ground state recovery times of these two species in fully oxygenated and deoxygenated bovine whole blood to be 3.7±0.8  ns and 7.9±1.0  ns, respectively. Hence, even very closely related pairs of molecules may be differentiated with this technique.

The molecular structure and absorption spectrum of hydroxy substituted dibenzoylmethanatoboron difluoride in solution: A theoretical and experimental study

NASA Astrophysics Data System (ADS)

Gelfand, Natalia; Freidzon, Alexandra; Fedorenko, Elena

2018-01-01

Electronic spectroscopy and quantum chemistry are used to study the structure and absorption spectra of the hydroxy substituted dibenzoylmethanatoboron difluoride (OHDBMBF2) in solutions. Introducing a hydroxy group in the diketonate moiety allows the dye to form intermolecular complexes with proton acceptors, such as solvents or analytes, thus making it a promising chemical sensor. Our calculations show that donor oxygen-containing solvents break the intramolecular hydrogen bond Osbnd H···Odik and form an intermolecular Osbnd H···Osolv bond thus disrupting the coplanarity of the dye and affecting the position and shape of its absorption bands. The spectra calculated with explicit solvent combined with polarizable continuum model (PCM) better agree with the experiment than those calculated only within PCM.

Electronic structure differences between H(2)-, Fe-, Co-, and Cu-phthalocyanine highly oriented thin films observed using NEXAFS spectroscopy.

PubMed

Willey, T M; Bagge-Hansen, M; Lee, J R I; Call, R; Landt, L; van Buuren, T; Colesniuc, C; Monton, C; Valmianski, I; Schuller, Ivan K

2013-07-21

Phthalocyanines, a class of macrocyclic, square planar molecules, are extensively studied as semiconductor materials for chemical sensors, dye-sensitized solar cells, and other applications. In this study, we use angular dependent near-edge x-ray absorption fine structure (NEXAFS) spectroscopy as a quantitative probe of the orientation and electronic structure of H2-, Fe-, Co-, and Cu-phthalocyanine molecular thin films. NEXAFS measurements at both the carbon and nitrogen K-edges reveal that phthalocyanine films deposited on sapphire have upright molecular orientations, while films up to 50 nm thick deposited on gold substrates contain prostrate molecules. Although great similarity is observed in the carbon and nitrogen K-edge NEXAFS spectra recorded for the films composed of prostrate molecules, the H2-phthalocyanine exhibits the cleanest angular dependence due to its purely out-of-plane π* resonances at the absorption onset. In contrast, organometallic-phthalocyanine nitrogen K-edges have a small in-plane resonance superimposed on this π* region that is due to a transition into molecular orbitals interacting with the 3dx(2)-y(2) empty state. NEXAFS spectra recorded at the metal L-edges for the prostrate films reveal dramatic variations in the angular dependence of specific resonances for the Cu-phthalocyanines compared with the Fe-, and Co-phthalocyanines. The Cu L3,2 edge exhibits a strong in-plane resonance, attributed to its b1g empty state with dx(2)-y(2) character at the Cu center. Conversely, the Fe- and Co- phthalocyanine L3,2 edges have strong out-of-plane resonances; these are attributed to transitions into not only b1g (dz(2)) but also eg states with dxz and dyz character at the metal center.

Performance impact of novel polymeric dyes in photoresist applications

NASA Astrophysics Data System (ADS)

Lu, Ping-Hung; Mehtsun, Salem; Sagan, John P.; Shan, Jianhui; Gonzalez, Eleazar; Ding, Shuji; Khanna, Dinesh N.

1999-06-01

Dye compounds are commonly used in photoresists as a low cost and effective way to control swing and/or standing wave effect caused by thin film interference as well as reflective notching by reflective light from highly reflective substrate and topography. Convention dyes are typically a monomeric compound with high absorptivity at the wavelength of exposure light and compatible with the resist system selected. Because of the monomeric nature, conventional dyes are relatively low in molecular weight hence their thermal stability and sublimination propensity has always been an issue of concern. We recently synthesize several highly thermal stable diazotized polymeric dyes. Their thermal properties as well as compatibility with resist system were investigated. The impact of polymeric dyes on the resists lithographic performance, swing reduction and reflective notching control are discussed.

The role of intestinal microflora in the activation of benzidine and benzidine congener based dyes

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

Cerniglia, C.E.; Franklin, W.; Campbell, W.L.

1988-09-01

Benzidine-based dyes are widely used in the dye manufacturing, textile dyeing, color paper printing and leather industries. Some benzidine based dyes have been shown to be carcinogenic due to their biotransformation in the liver or in the gastrointestinal tract to benzidine, a long recognized human urinary bladder carcinogen. Occupational exposure to workers can be through skin absorption, inhalation and ingestion of the benzidine based dyes. Previous studies of benzidine based dye metabolism have shown that enzymatic reduction of the azo group, yielding benzidine is an essential step in the activation of these compounds to genotoxic species. Azo reduction activity ismore » present in both the liver and gastrointestinal tract and little is known whether the first step in the toxification process of benzidine based dyes occurs at either site. They are investigating the capacity of intestinal microflora to metabolize benzidine-based dyes and determine their overall importance in the activation of this class of industrially important chemicals.« less

Interaction of dyes CD–1 and SD–1 with the surface of oligodimethysiloxane

NASA Astrophysics Data System (ADS)

Chausov, D. N.

2018-03-01

We carried out the modeling orientation of the dyes CD–1 and SD–1 relative to the surface of oligodimethysiloxane using the atom–atom potentials method. We have discovered the dependence of the interaction energy in dyes molecules on the angles which characterizes their orientation relative to the surface of the oligodimethysiloxane crystal. It was found out that the obtained energy value of interaction with the surface can explain weak adhesive qualities of the dyes and the orientation type relative to the surface. We identified the break– loose force for the dyes on the oligodimethysiloxane crystal surface.

Heterogeneous Electron-Transfer Dynamics through Dipole-Bridge Groups.

PubMed

Nieto-Pescador, Jesus; Abraham, Baxter; Li, Jingjing; Batarseh, Alberto; Bartynski, Robert A; Galoppini, Elena; Gundlach, Lars

2016-01-14

Heterogeneous electron transfer (HET) between photoexcited molecules and colloidal TiO 2 has been investigated for a set of Zn-porphyrin chromophores attached to the semiconductor via linkers that allow to change level alignment by 200 meV by reorientation of the dipole moment. These unique dye molecules have been studied by femtosecond transient absorption spectroscopy in solution and adsorbed on the TiO 2 colloidal film in vacuum. In solution energy transfer from the excited chromophore to the dipole group has been identified as a slow relaxation pathway competing with S 2 -S 1 internal conversion. On the film heterogeneous electron transfer occurred in 80 fs, much faster compared to all intramolecular pathways. Despite a difference of 200 meV in level alignment of the excited state with respect to the semiconductor conduction band, identical electron transfer times were measured for different linkers. The measurements are compared to a quantum-mechanical model that accounts for electronic-vibronic coupling and finite band width for the acceptor states. We conclude that HET occurs into a distribution of transition states that differs from regular surface states or bridge mediated states.

Electron impact excitation of the merocyanine molecule in the gas phase

NASA Astrophysics Data System (ADS)

Kulinich, A. V.; Ishchenko, A. A.; Kukhta, I. N.; Mitryukhin, L. K.; Kazakov, S. M.; Kukhta, A. V.

2018-03-01

Electronic transitions in a merocyanine dye were studied in the gas phase using electron energy loss spectroscopy and compared with the optical absorption spectra. It was found that the most intense band of the S1 ← S0 polymethine transition lies at 2.8 eV in vapor and 2.4 eV in n-hexane. Higher electronic transitions in the range of 3.7-7 eV were also analyzed. Besides, the singlet-triplet transition was revealed near 1.8 eV. TDDFT simulation of singlet-singlet transitions in the studied molecule was performed using B97D3, B3LYP, B3PW91 and wB97xD functionals. The calculated energy of the long-wavelength transition is closest to the experimental value with the latter. Other functionals result in the energy 0.2-0.4 eV exceeding experimental. The interpretation of higher transitions/bands is complicated due to their superposition and difference between experimental and calculated data. The excitation anisotropy spectra were measured in glycerol for more reliable determination of higher transitions and comparison with the TDDFT/PCM simulation.

Influence of the sign of the coupling on the temperature dependence of optical properties of one-dimensional exciton models

NASA Astrophysics Data System (ADS)

Cruzeiro, L.

2008-10-01

A new physical cause for a temperature-dependent double peak in exciton systems is put forward within a thermal equilibrium approach for the calculation of optical properties of exciton systems. Indeed, it is found that one-dimensional exciton systems with only one molecule per unit cell can have an absorption spectrum characterized by a double peak provided that the coupling between excitations in different molecules is positive. The two peaks, whose relative intensities vary with temperature, are located around the exciton band edges, being separated by an energy of approximately 4V, where V is the average coupling between nearest neighbours. For small amounts of diagonal and off-diagonal disorder, the contributions from the intermediate states in the band are also visible as intermediate structure between the two peaks, this being enhanced for systems with periodic boundary conditions. At a qualitative level, these results correlate well with experimental observations in the molecular aggregates of the thiacarbocyanine dye THIATS and in the organic crystals of acetanilide and N-methylacetamide.

Porous glass makes effective substrate for ozone-sensing reagent

NASA Technical Reports Server (NTRS)

1965-01-01

Porous-glass substrate is used for absorption of a dye used in measuring the concentration of atmospheric ozone at high altitudes. This measurement is based on the chemiluminescence produced in the reaction between ozone and the dye, rhodamine B. The porous glass provides a large interstitial surface area which promotes this reaction.

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.

Synthesis, Spectrofluorometric Studies, Micellization and non Linear Optical Properties of Blue Emitting Quinoline (AMQC) Dye.

PubMed

Afzal, S M; Asiri, Abdullah M; Razvi, M A N; Bakry, Ahmed H; Khan, Salman A; Zayed, Mohie E M

2016-03-01

Blue emitting 2-amino-4-(3, 4, 5-tri methoxyphenyl)-9-methoxy-5,6 dihydrobenzo[f]isoquinoline-1-carbonitrile (AMQC) dye was synthesized by one-pot multicomponent reactions (MCRs) of 3,4,5-trimethoxybenzaldehyd, malononitrile, 6-methoxy-1,2,3,4-tetrahydro-naphthalin-1-one and ammonium acetate. Results obtained from spectroscopic and elemental analysis of synthesized AMQC was in good agreement with their chemical structures. Fluorescence polarity study demonstrated that AMQC was sensitive to the polarity of the microenvironment provided by different solvents. In addition, spectroscopic and physicochemical parameters, including electronic absorption, excitation coefficient, stokes shift, oscillator strength, transition dipole moment and fluorescence quantum yield were investigated in order to explore the analytical potential of AMQC. Dye undergoes solubilization in different micelles and may be used as a quencher and a probe to determine the critical micelle concentration (CMC) of SDS and CTAB. Nonlinear optical parameters of AMQC dye shows relatively lower nonlinear refractive index and nonlinear absorption coefficient at the power levels. Variation of n2 with concentration is linear in the concentration range used in the present study.

Dye adsorbates BrPDI, BrGly, and BrAsp on anatase TiO2(001) for dye-sensitized solar cell applications

NASA Astrophysics Data System (ADS)

Çakır, D.; Gülseren, O.; Mete, E.; Ellialtıoǧlu, Ş.

2009-07-01

Using the first-principles plane-wave pseudopotential method within density functional theory, we systematically investigated the interaction of perylenediimide (PDI)-based dye compounds (BrPDI, BrGly, and BrAsp) with both unreconstructed (UR) and reconstructed (RC) anatase TiO2(001) surfaces. All dye molecules form strong chemical bonds with surface in the most favorable adsorption structures. In UR-BrGly, RC-BrGly, and RC-BrAsp cases, we have observed that highest occupied molecular orbital and lowest unoccupied molecular orbital levels of molecules appear within band gap and conduction-band region, respectively. Moreover, we have obtained a gap narrowing upon adsorption of BrPDI on the RC surface. Because of the reduction in effective band gap of surface-dye system and possibly achieving the visible-light activity, these results are valuable for photovoltaic and photocatalytic applications. We have also considered the effects of hydration of surface to the binding of BrPDI. It has been found that the binding energy drops significantly for the completely hydrated surfaces.

Electric field assisted sintering to improve the performance of nanostructured dye sensitized solar cell (DSSC)

NASA Astrophysics Data System (ADS)

Shojaeifar, Mohsen; Mohajerani, Ezeddin; Fathollahi, Mohammadreza

2018-01-01

Herein, we report the application of electric field assisted sintering (EFAS) procedure in dye sensitized solar cells (DSSCs). The EFAS process improved DSSC performance by enhancing optical and electrical characteristics simultaneously. The EFAS procedure is shown to be capable of reducing the TiO2 nanoparticle aggregation leading to the higher surface area for dye molecules adsorbates. Lower nanoparticle aggregation can be evidently observed by field emission scanning electron microscopy imaging. By applying an external electric field, the current density and conversion efficiency improved significantly about 30% and 45%, respectively. UV-Visible spectra of the desorbed dye molecules on the porous nanoparticles bedding confirm a higher amount of dye loading in the presence of an external electric field. Correspondingly, comprehensive J-V characteristics modeling reveals the enhancement of the diffusion coefficient by EFAS process. The proposed method can be applied to improve the efficiency of the mesostructured hybrid perovskite solar cells, photodetectors, and quantum dot-sensitized solar cells, as well as reduction of the surface area loss in all porous media.

Oxazine dye-conjugated dna oligonucleotides: Förster resonance energy transfer in view of molecular dye-DNA interactions.

PubMed

Kupstat, Annette; Ritschel, Thomas; Kumke, Michael U

2011-12-21

In this work, the photophysical properties of two oxazine dyes (ATTO 610 and ATTO 680) covalently attached via a C6-amino linker to the 5'-end of short single-stranded as well as double-stranded DNA (ssDNA and dsDNA, respectively) of different lengths were investigated. The two oxazine dyes were chosen because of the excellent spectral overlap, the high extinction coefficients, and the high fluorescence quantum yield of ATTO 610, making them an attractive Förster resonance energy transfer (FRET) pair for bioanalytical applications in the far-red spectral range. To identify possible molecular dye-DNA interactions that cause photophysical alterations, we performed a detailed spectroscopic study, including time-resolved fluorescence anisotropy and fluorescence correlation spectroscopy measurements. As an effect of the DNA conjugation, the absorption and fluorescence maxima of both dyes were bathochromically shifted and the fluorescence decay times were increased. Moreover, the absorption of conjugated ATTO 610 was spectrally broadened, and a dual fluorescence emission was observed. Steric interactions with ssDNA as well as dsDNA were found for both dyes. The dye-DNA interactions were strengthened from ssDNA to dsDNA conjugates, pointing toward interactions with specific dsDNA domains (such as the top of the double helix). Although these interactions partially blocked the dye-linker rotation, a free (unhindered) rotational mobility of at least one dye facilitated the appropriate alignment of the transition dipole moments in doubly labeled ATTO 610/ATTO 680-dsDNA conjugates for the performance of successful FRET. Considering the high linker flexibility for the determination of the donor-acceptor distances, good accordance between theoretical and experimental FRET parameters was obtained. The considerably large Förster distance of ~7 nm recommends the application of this FRET pair not only for the detection of binding reactions between nucleic acids in living cells but also for monitoring interactions of larger biomolecules such as proteins.

DFT Study of the Structure, Reactivity, Natural Bond Orbital and Hyperpolarizability of Thiazole Azo Dyes

PubMed Central

Osman, Osman I.

2017-01-01

The structure, reactivity, natural bond orbital (NBO), linear and nonlinear optical (NLO) properties of three thiazole azo dyes (A, B and C) were monitored by applying B3LYP, CAM-B3LYP and ωB97XD functionals with 6-311++G** and aug-cc-pvdz basis sets. The geometrical parameters, dipole moments, HOMO-LUMO (highest occupied molecular orbital, lowest unoccupied molecular orbital) energy gaps, absorption wavelengths and total hyperpolarizabilities were investigated in carbon tetrachloride (CCl4) chloroform (CHCl3), dichloromethane (CH2Cl2) and dimethlysulphoxide (DMSO). The donor methoxyphenyl group deviates from planarity with the thiazole azo moiety by ca. 38°; while the acceptor dicyanovinyl, indandione and dicyanovinylindanone groups diverge by ca. 6°. The HOMOs for the three dyes are identical. They spread over the methoxyphenyl donor moiety, the thiazole and benzene rings as π-bonding orbitals. The LUMOs are shaped up by the nature of the acceptor moieties. The LUMOs of the A, B and C dyes extend over the indandione, malononitrile and dicyanovinylindanone acceptor moieties, respectively, as π-antibonding orbitals. The HOMO-LUMO splittings showed that Dye C is much more reactive than dyes A and B. Compared to dyes A and B, Dye C yielded a longer maximum absorption wavelength because of the stabilization of its LUMOs relative to those of the other two. The three dyes show solvatochromism accompanied by significant increases in hyperpolarizability. The enhancement of the total hyperpolarizability of C compared to those of A and B is due to the cumulative action of the long π-conjugation of the indanone ring and the stronger electron-withdrawing ability of the dicyanovinyl moiety that form the dicyanovinylindanone acceptor group. These findings are facilitated by a natural bond orbital (NBO) technique. The very high total hyperpolarizabilities of the three dyes define their potent nonlinear optical (NLO) behaviour. PMID:28157151

Optical Properties of Vibronically Coupled Cy3 Dimers on DNA Scaffolds.

PubMed

Cunningham, Paul D; Kim, Young C; Díaz, Sebastián A; Buckhout-White, Susan; Mathur, Divita; Medintz, Igor L; Melinger, Joseph S

2018-05-17

We examine the effect of electronic coupling on the optical properties of Cy3 dimers attached to DNA duplexes as a function of base pair (bp) separation using steady-state and time-resolved spectroscopy. For close Cy3-Cy3 separations, 0 and 1 bp between dyes, intermediate to strong electronic coupling is revealed by modulation of the absorption and fluorescence properties including spectral band shape, peak wavelength, and excited-state lifetime. Using a vibronic exciton model, we estimate coupling strengths of 150 and 266 cm -1 for the 1 and 0 bp separations, respectively, which are comparable to those found in natural light-harvesting complexes. For the strongest electronic coupling (0 bp separation), we observe that the absorption band shape is strongly affected by the base pairs that surround the dyes, where more strongly hydrogen-bonded G-C pairs produce a red-shifted absorption spectrum consistent with a J-type dimer. This effect is studied theoretically using molecular dynamics simulation, which predicts an in-line dye configuration that is consistent with the experimental J-type spectrum. When the Cy3 dimers are in a standard aqueous buffer, the presence of relatively strong electronic coupling is accompanied by decreased fluorescence lifetime, suggesting that it promotes nonradiative relaxation in cyanine dyes. However, we show that the use of a viscous solvent can suppress this nonradiative recombination and thereby restore the dimer fluorescent emission. Ultrafast transient absorption measurements of Cy3 dimers in both standard aqueous buffer and viscous glycerol buffer suggest that sufficiently strong electronic coupling increases the probability of excited-state relaxation through a dark state that is related to Cy3 torsional motion.

Probes labelled with energy transfer coupled dyes

DOEpatents

Mathies, R.A.; Glazer, A.; Ju, J.

1997-11-18

Compositions are provided comprising sets of fluorescent labels carrying pairs of donor and acceptor dye molecules, designed for efficient excitation of the donors at a single wavelength and emission from the acceptor in each of the pairs at different wavelengths. The different molecules having different donor-acceptor pairs can be modified to have substantially the same mobility under separation conditions, by varying the distance between the donor and acceptor in a given pair. Particularly, the fluorescent compositions find use as labels in sequencing nucleic acids. 7 figs.

Probes labelled with energy transfer coupled dyes

DOEpatents

Mathies, Richard A.; Glazer, Alexander; Ju, Jingyue

1997-01-01

Compositions are provided comprising sets of fluorescent labels carrying pairs of donor and acceptor dye molecules, designed for efficient excitation of the donors at a single wavelength and emission from the acceptor in each of the pairs at different wavelengths. The different molecules having different donor-acceptor pairs can be modified to have substantially the same mobility under separation conditions, by varying the distance between the donor and acceptor in a given pair. Particularly, the fluorescent compositions find use as labels in sequencing nucleic acids.

A Blue Diketopyrrolopyrrole Sensitizer with High Efficiency in Nickel-Oxide-based Dye-Sensitized Solar Cells.

PubMed

Farré, Yoann; Raissi, Mahfoudh; Fihey, Arnaud; Pellegrin, Yann; Blart, Errol; Jacquemin, Denis; Odobel, Fabrice

2017-06-22

We prepared a series of four new diketopyrrolopyrroles (DPPs)-based sensitizers that exhibit high-molar extinction coefficients, extended absorption into the long wavelengths, and well-suited photoredox properties to act as sensitizers in p-type dye-sensitized solar cells (p-DSSCs). These new DPP dyes, composed of a thienyl DPP core, are substituted on one end either by a thiophene carboxylic (Th) or a 4,4'-[(phenyl)aza]dibenzoic acid as anchoring group and, on the other extremity, either by a proton or a naphthalene diimide (NDI) moiety. These new dyes were completely characterized by absorption and emission spectroscopy along with electrochemistry and they were modeled by time-dependent DFT (TD-DFT) quantum chemical calculations. The photovoltaic study in p-DSSC with iodine-based electrolyte reveals that the Th-DPP-NDI dye is particularly efficient (J sc =7.38 mA cm -2 ; V oc =147 mV; FF=0.32; η=0.35 %) and quite active in the low-energy region of the solar spectrum (above 700 nm), where only a few NiO dyes are effective. To illustrate the potential of DPP dyes in photocathodes, we designed a highly efficient tandem DSSC composed of a TiO 2 photoanode sensitized by the dye D35 and a NiO photocathode sensitized by Th-DPP-NDI. This tandem DSSC gives the highest performances ever reported (J sc =6.73 mA cm -2 ; V oc =910 mV; η=4.1 %) and, importantly, the tandem cell outcompetes with the sub-cells. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectral characteristics and photosensitization of TiO2 nanoparticles in reverse micelles by perylenes.

PubMed

Hernández, Laura I; Godin, Robert; Bergkamp, Jesse J; Llansola Portolés, Manuel J; Sherman, Benjamin D; Tomlin, John; Kodis, Gerdenis; Méndez-Hernández, Dalvin D; Bertolotti, Sonia; Chesta, Carlos A; Mariño-Ochoa, Ernesto; Moore, Ana L; Moore, Thomas A; Cosa, Gonzalo; Palacios, Rodrigo E

2013-04-25

We report on the photosensitization of titanium dioxide nanoparticles (TiO2 NPs) synthesized inside AOT (bis(2-ethylhexyl) sulfosuccinate sodium salt) reverse micelles following photoexcitation of perylene derivatives with dicarboxylate anchoring groups. The dyes, 1,7-dibromoperylene-3,4,9,10-tetracarboxy dianhydride (1), 1,7-dipyrrolidinylperylene-3,4,9,10-tetracarboxy dianhydride (2), and 1,7-bis(4-tert-butylphenyloxy)perylene-3,4,9,10-tetracarboxy dianhydride (3), have considerably different driving forces for photoinduced electron injection into the TiO2 conduction band, as estimated by electrochemical measurements and quantum mechanical calculations. Fluorescence anisotropy measurements indicate that dyes 1 and 2 are preferentially solubilized in the micellar structure, creating a relatively large local concentration that favors the attachment of the dye to the TiO2 surface. The binding process was followed by monitoring the hypsochromic shift of the dye absorption spectra over time for 1 and 2. Photoinduced electron transfer from the singlet excited state of 1 and 2 to the TiO2 conduction band (CB) is indicated by emission quenching of the TiO2-bound form of the dyes and confirmed by transient absorption measurements of the radical cation of the dyes and free carriers (injected electrons) in the TiO2 semiconductor. Steady state and transient spectroscopy indicate that dye 3 does not bind to the TiO2 NPs and does not photosensitize the semiconductor. This observation was rationalized as a consequence of the bulky t-butylphenyloxy groups which create a strong steric impediment for deep access of the dye within the micelle structure to reach the semiconductor oxide surface.

Identification of Biomarkers Associated with the Healing of Chronic Wounds

DTIC Science & Technology

2015-11-01

The analysis of the wound fluid began with a broad survey tool Kinex™ Antibody Microarray (KAM) a single dye , non-competitive sample binding...signaling proteins. Lysate protein from each sample was covalently labeled with a fluorescent dye combination. Free dye molecules were then...patterned structures is controlled by varying their pattern geometry. The biodegradation of micro-patterned structures is modeled geometrically based on

[pH sensors based on rubbery ormosils preparation and their spectrum studies].

PubMed

Chen, Xi; Dai, Yuan-jing; Li, Wei; Zhuang, Zhi-xia; Wang, Xiao-ru

2002-02-01

A new type of methyl substituted ormosils as a matrix for bromophenol blue (BPhB) and bromocresol green (BCG) is described. The new ormosils combine features of classical TEOS sol-gel material such as solvability in organic solvent and those of sol-gel glasses such as transparent and a porous structure, the ormosils also make a good mechanical stability. The influence of the conditions during the polymerisation process on the photochemical properties of BPhB and BCG has been studied. This sol-gel material was wed to immobilize pH-sensitive absorption dyes, bromothymol blue and bromocresol green, to prepare pH sensing films. The several aspects of the sensing films, including the leaching of the dye from gel, response time to different pH buffer solution, absorption spectra and the improvement of the immobilization of the dyes to filmo, were also discussed.

Proton Induced Modulation of ICT and PET Processes in an Imidazo-phenanthroline Based BODIPY Fluorophores.

PubMed

Thakare, Shrikant S; Chakraborty, Goutam; Kothavale, Shantaram; Mula, Soumyaditya; Ray, Alok K; Sekar, Nagaiyan

2017-11-01

BODIPY fluorophores linked with an imidazo-phenanthroline donor at α and β positions have been synthesized. Intriguing intramolecular charge transfer phenomenon is observed in both the dyes which has been extensively investigated using UV-vis absorption, steady-state and time-resolved fluorescence measurements. H-bonding and intrinsic polarity of the solvents has modulated the absorption and emission bands of these fluorophores strongly causing significant increase in the Stokes shifts. In spite of having difference only in terms of the position of donor subunit, the photophysics of these dyes are not only significantly different from each other, but contradictory too. Interestingly, acidochromic studies revealed the shuttling mechanism between ICT and PET processes for BDP 2. Quantum chemical calculations have been employed further to support experimental findings. DFT and TD-DFT method of analysis have been used to optimize ground and excited state geometries of the synthesized dyes.

The brilliant blue FCF ion-molecular forms in solutions according to the spectrophotometry data

NASA Astrophysics Data System (ADS)

Chebotarev, A. N.; Bevziuk, K. V.; Snigur, D. V.; Bazel, Ya. R.

2017-10-01

The brilliant blue FCF acid-base properties in aqueous solutions have been studied and its ionization constants have been defined by tristimulus colorimetry and spectrophotometry methods. The scheme of the acid-base dye equilibrium has been proposed and a diagram of the distribution of its ionic-molecular forms has been built. It has been established that the dominant form of the dye was the electroneutral form, which molar absorptivity (ɛ625 = 0.97 × 105) increases with the increase of the dielectric permittivity of the solvent. It has been shown that the replacement of polar solvents by less polar ones is causing a bathochromic shift of the maximum absorption band of the dye, the value of which is correlated with the value of the Hansen parameter. Tautomerization constants have been defined in a number of solvents and associated with the value of the Dimroth-Reichardt parameter.

Photophysical behavior of new acridine(1,8)dione dyes.

PubMed

Cabanzo Hernández, Rafael; David Gara, Pedro M; Velasco, Daniel Molina; Erra-Balsells, Rosa; Bilmes, Gabriel M

2013-11-01

The photophysical behavior of five acridine(1,8)dione dyes of biological interest was studied by absorption and fluorescence spectroscopy, photoacoustics and time resolved phosphorescence techniques. The results obtained in ethanol and acetonitrile solutions show that the main spectroscopic and photophysical parameters of these compounds depend strongly on both the solvent and oxygen concentrations. Oxygen completely quenched the triplet state of all dyes. In nitrogen-saturated solutions, quantum efficiencies of triplet formation in ethanol were lower than those in acetonitrile.

Strength of interactions between immobilized dye molecules and sol-gel matrices.

PubMed

Ismail, Fanya; Schoenleber, Monika; Mansour, Rolan; Bastani, Behnam; Fielden, Peter; Goddard, Nicholas J

2011-02-21

In this paper we present a new theory to re-examine the immobilization technique of dye doped sol-gel films, define the strength and types of possible bonds between the immobilized molecule and sol-gel glass, and show that the immobilized molecule is not free inside the pores as was previously thought. Immobilizing three different pH sensitive dyes with different size and functional groups inside the same sol-gel films revealed important information about the nature of the interaction between the doped molecule and the sol-gel matrix. The samples were characterized by means of ultraviolet-visible spectrophotometer (UV-VIS), thermal gravimetric analysis (TGA), mercury porosimetry (MP), nuclear magnetic resonance spectroscopy ((29)Si NMR) and field-emission environmental scanning electron microscopy (ESEM-FEG). It was found that the doped molecule itself has a great effect on the strength and types of the bonds. A number of factors were identified, such as number and types of the functional groups, overall charge, size, pK(a) and number of the silanol groups which surround the immobilized molecule. These results were confirmed by the successful immobilization of bromocresol green (BCG) after a completely polymerized sol-gel was made. The sol-gel consisted of 50% tetraethoxysilane (TEOS) and 50% methyltriethoxysilane (MTEOS) (w/w). Moreover, the effect of the immobilized molecule on the structure of the sol-gel was studied by means of a leaky waveguide (LW) mode for doped films made before and after polymerization of the sol-gel.

Optical Fluorescent Imaging to Monitor Temporal Effects of Microbubble-Mediated Ultrasound Therapy

PubMed Central

Sorace, Anna G.; Saini, Reshu; Rosenthal, Eben; Warram, Jason M.; Zinn, Kurt R.; Hoyt, Kenneth

2013-01-01

Microbubble-mediated ultrasound therapy can noninvasively enhance drug delivery to localized regions in the body. This technique can be beneficial in cancer therapy, but currently there are limitations to tracking the therapeutic effects. The purpose of this experiment was to investigate the potential of fluorescent imaging for monitoring the temporal effects of microbubble-mediated ultrasound therapy. Mice were implanted with 2LMP breast cancer cells. The animals underwent microbubble-mediated ultrasound therapy in the presence of Cy5.5 fluorescent-labeled IgG antibody (large molecule) or Cy5.5 dye (small molecule) and microbubble contrast agents. Control animals were administered fluorescent molecules only. Animals were transiently imaged in vivo at 1, 10, 30, and 60 min post therapy using a small animal optical imaging system. Tumors were excised and analyzed ex vivo. Tumors were homogenized and emulsion imaged for Cy5.5 fluorescence. Monitoring in vivo results showed significant influx of dye into the tumor (p < 0.05) using the small molecule, but not in the large molecule group (p > 0.05). However, after tumor emulsion, significantly higher dye concentration was detected in therapy group tumors for both small and large molecule groups in comparison to their control counterparts (p < 0.01). This paper explores a noninvasive optical imaging method for monitoring the effects of microbubble-mediated ultrasound therapy in a cancer model. It provides temporal information following the process of increasing extravasation of molecules into target tumors. PMID:23357902