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.

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).

Imaging the Ultrafast Photoelectron Transfer Process in Alizarin-TiO2.

PubMed

Gomez, Tatiana; Hermann, Gunter; Zarate, Ximena; Pérez-Torres, Jhon Fredy; Tremblay, Jean Christophe

2015-07-30

In this work, we adopt a quantum mechanical approach based on time-dependent density functional theory (TDDFT) to study the optical and electronic properties of alizarin supported on TiO2 nano-crystallites, as a prototypical dye-sensitized solar cell. To ensure proper alignment of the donor (alizarin) and acceptor (TiO2 nano-crystallite) levels, static optical excitation spectra are simulated using time-dependent density functional theory in response. The ultrafast photoelectron transfer from the dye to the cluster is simulated using an explicitly time-dependent, one-electron TDDFT ansatz. The model considers the δ-pulse excitation of a single active electron localized in the dye to the complete set of energetically accessible, delocalized molecular orbitals of the dye/nano-crystallite complex. A set of quantum mechanical tools derived from the transition electronic flux density is introduced to visualize and analyze the process in real time. The evolution of the created wave packet subject to absorbing boundary conditions at the borders of the cluster reveal that, while the electrons of the aromatic rings of alizarin are heavily involved in an ultrafast charge redistribution between the carbonyl groups of the dye molecule, they do not contribute positively to the electron injection and, overall, they delay the process.

Controlled enzymatic cutting of DNA molecules adsorbed on surfaces using soft lithography

NASA Astrophysics Data System (ADS)

Auerbach, Alyssa; Budassi, Julia; Shea, Emily; Zhu, Ke; Sokolov, Jonathan

2013-03-01

The enzyme DNase I was applied to adsorbed and aligned DNA molecules (Lamda, 48.5 kilobase pairs (kbp), and T4, 165.6 kbp), stretched linearly on a surface, by stamping with a polydimethylsiloxane (PDMS) grating. The DNAs were cut by the enzyme into separated, micron-sized segments along the length of the molecules at positions determined by the grating dimensions (3-20 microns). Ozone-treated PDMS stamps were coated with DNase I solutions and placed in contact with surface-adsorbed DNA molecules deposited on a 750 polymethylmethacrylate (PMMA) film spun-cast onto a silicon substrate. The stamps were applied under pressure for times up to 15 minutes at 37 C. The cutting was observed by fluorescence microscopy imaging of DNA labeled with YOYO dye. Cutting was found to be efficient despite the steric hindrance due to surface attachment of the molecules. Methods for detaching and separating the cut segments for sequencing applications will be discussed. Supported by NSF-DMR program.

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.

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.

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.

Long vertically aligned titania nanotubes on transparent conducting oxide for highly efficient solar cells.

PubMed

Varghese, Oomman K; Paulose, Maggie; Grimes, Craig A

2009-09-01

Dye-sensitized solar cells consist of a random network of titania nanoparticles that serve both as a high-surface-area support for dye molecules and as an electron-transporting medium. Despite achieving high power conversion efficiencies, their performance is limited by electron trapping in the nanoparticle film. Electron diffusion lengths can be increased by transporting charge through highly ordered nanostructures such as titania nanotube arrays. Although titania nanotube array films have been shown to enhance the efficiencies of both charge collection and light harvesting, it has not been possible to grow them on transparent conducting oxide glass with the lengths needed for high-efficiency device applications (tens of micrometres). Here, we report the fabrication of transparent titania nanotube array films on transparent conducting oxide glass with lengths between 0.3 and 33.0 microm using a novel electrochemistry approach. Dye-sensitized solar cells containing these arrays yielded a power conversion efficiency of 6.9%. The incident photon-to-current conversion efficiency ranged from 70 to 80% for wavelengths between 450 and 650 nm.

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

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.

Photobleaching effect in azo-dye containing epoxy resin films: the potentiality of carbon nanotubes as azo-dye dispensers

NASA Astrophysics Data System (ADS)

Díaz Costanzo, Guadalupe; Goyanes, Silvia; Ledesma, Silvia

2015-04-01

Azo-dye molecules may suffer from bleaching under certain illumination conditions. When this photoinduced process occurs, it generates an irreversible effect that is characterized by the loss of absorption of the dye molecule. Moreover, the well-known isomerization of azodye molecules does not occur anymore. In this work it is shown how the addition of a small amount of multi-walled carbon nanotubes (MWCNTs) helps to decrease the bleaching effect in a photosensitive guest-host azo-polymer film. Two different systems were fabricated using an epoxy resin as polymer matrix. An azo-dye, Disperse Orange 3, was used as photosensitive material in both systems and MWCNTs were added into one of them. The optical response of the polymeric systems was studied considering the degree of photoinduced birefringence. Photobleaching of the azo-dye was observed in all cases however, the effect is lower for the composite material containing 0.2 wt % MWCNTs. The weak interaction between MWCNTs and dye molecules is less favorable when the material is heated. The optical behavior of the heated composite material suggests that carbon nanotubes can be potentially used as azo dye dispensers. The results are interpreted in terms of the non-covalent interaction between azo-dye molecules and MWCNTs.

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

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.

Optical properties of cyanine dyes in nanotubes of chrysotile asbestos

NASA Astrophysics Data System (ADS)

Starovoytov, Anton A.; Vartanyan, Tigran A.; Belotitskii, Vladimir I.; Kumzerov, Yuri A.; Sysoeva, Anna A.

2017-08-01

Optical properties of cyanine dye molecules incorporated in nanotubes of natural chrysotile asbestos are studied. The absorption and fluorescence spectra of dye in asbestos have the similar shapes as in the ethanol solution, apart from small blue shift of the maxima. The Stokes shift in asbestos is smaller than in the ethanol solution. The fluorescence decay times of the dyes in asbestos nanotubes are found to be larger than that in the case of thin films of the same dyes formed on the transparent dielectric supports. This observation is rationalized in terms of the stereoisomerization hindrance in the excited electronic state of dye molecules. At the same time linear dichroism and fluorescence anisotropy observed in the experiment indicate that the embedded dye molecules are well-isolated monomer oriented predominantly along asbestos nanotubes.

Enhanced absorption in a reverse saturable absorbing dye blended with carbon nanotubes.

PubMed

Webster, Scott; Reyes-Reyes, Marisol; Williams, Richard; Carroll, David L

2008-12-01

Using nonlinear absorption at 532 nm in the nanosecond temporal regime, we have measured the low fluence nonlinear transmittance properties of the reverse saturable absorbing carbocyanine dye, 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide (HITCI), blended with well dispersed carbon nanotubes. The nonlinear optical properties of the blends are strongly dependent on the ratio of dye to nanotubes in solution. In the case where the nanotubes per dye molecule ratio is large, we see a distinctive enhancement in optical fluence limiting properties of the system, suggesting enhanced absorption of the excited states. However, when the nanotube to dye ratio decreases, the system's response is dominated by the behavior of the dye. We suggest that this can be understood as a two component system in which sensitized dye molecules associated with the nanotubes have an effectively different optical cross-section from the dye molecules far from the nanotubes. From classical antennae considerations, this is expected.

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

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.

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

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.

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.

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.

Effect of DNA-CTMA complex on optical properties of LDS 821 dye

NASA Astrophysics Data System (ADS)

Udayan, Sony; Ramachandran, Vijesh Kavumoottil; Sebastian, Mathew; Chandran, Pradeep; Nampoori, Vadakkedath Parameswaran Narayanan; Thomas, Sheenu

2017-07-01

We have investigated the fluorescence behavior of LDS 821 dye (Styryl 9 M) with deoxyribonucleic acid attached with cetyltrimethyl-ammonium (DNA-CTMA). Optical absorption studies confirm the intercalation of the dye molecules with DNA-CTMA. Fluorescence studies show an enhancement of fluorescence intensity of dye with DNA-CTMA, which suggest the reduction of TICT states of the dye molecule. The FWHM of the fluorescence spectrum increases from 95 nm to 161 nm indicating the formation of new energy levels when DNA-CTMA forms a complex with LDS 821 dye. Fluorescence lifetime measurements shows that lifetime of LDS 821 varies from 507ps to 953 ps with the addition of DNA-CTMA, which also confirms the deactivation of TICT states of dye molecule. Results show that the incorporation of DNA-CTMA with LDS 821 dye improves the optical characteristics of LDS 821 dye and therefore, can be used as a good fluorescence probe for DNA visualization as well as in lasing applications.

Electronic and chemical structure of an organic light emitter embedded in an inorganic wide-bandgap semiconductor: Photoelectron spectroscopy of layered and composite structures of Ir(BPA) and ZnSe

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

Dimamay, Mariel; Laboratoire de Chimie des Polymères Organiques, CNRS, Université de Bordeaux, UMR 5629-16 Avenue Pey-Berland, 33607 Pessac; Mayer, Thomas

Luminescent organic phases embedded in conductive inorganic matrices are proposed for hybrid organic-inorganic light-emitting diodes. In this configuration, the organic dye acts as the radiative recombination site for charge carriers injected into the inorganic matrix. Our investigation is aimed at finding a material combination where the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the organic dye are situated in between the valence and conduction bands of the inorganic matrix in order to promote electron and hole transfer from the matrix to the dye. Bilayer and composite thin films of zinc selenide (ZnSe) and a redmore » iridium complex (Ir(BPA)) organic light emitter were prepared in situ via UHV thermal evaporation technique. The electronic and atomic structures were studied applying X-ray and ultraviolet photoelectron spectroscopies. The measured energy band alignments for the ZnSe/Ir(BPA) bilayer and ZnSe+Ir(BPA) composite reveal that the HOMO and LUMO of the organic dye are positioned in the ZnSe bandgap. For the initial steps of ZnSe deposition on a dye film to form Ir(BPA)/ZnSe bilayers, zinc atoms intercalate into the dye film leaving behind an excess of selenium at the interface that partly reacts with dye molecules. Photoelectron spectroscopy of the composites shows the same species suggesting a similar mechanism. This mechanism leads to composite films with increased content of amorphous phases in the inorganic matrix, thereby affecting its conductivity, as well as to the presence of nonradiative recombination sites provided by the intercalated Zn atoms.« less

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.

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.

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.

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.

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

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

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.

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.

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.

Measurement of photoluminescence from a twisted-nematic liquid crystal/dye cell for an application in an energy-harvesting display

NASA Astrophysics Data System (ADS)

Ohta, Masamichi; Itaya, Shunsuke; Ozawa, Shintaro; Binti, M. Azmi; Dianah, Nada; Fujieda, Ichiro

2016-09-01

One can convert a Luminescent Solar Concentrator (LSC) to an energy-harvesting display by scanning a laser beam on it. By incorporating a guest-host system of liquid crystal (LC) and dye materials in an LSC, the power of photoluminescence (PL) utilized for either display or energy-harvesting can be adjusted to the changes in ambient lighting conditions. We have measured basic characteristics of an LC/dye cell with twisted-nematic (TN) alignment. These are absorption of the laser light, PL radiation pattern, contrast of luminance, spreading of the PL generated by a narrow laser beam, and their dependencies on the bias. The results are similar to those of the LC/dye cell with antiparallel (AP) alignment with the following exceptions. First, absorption by the TN cell depends on the bias for both polarization components of the excitation light, while the AP cell exhibits a bias dependency only for the component polarized along the alignment direction. Second, the PL from the TN cell is mostly polarized along the alignment direction on the exit side of the cell while the PL from the AP cell is mostly polarized along its alignment direction. These observations can be attributed to the fact that the polarization plane of a linearly polarized light rotates as it propagated the TN-LC layer. For both AP and TN cells, low-intensity PL is observed from the whole cell surfaces. This can degrade the contrast of a displayed image. Bias application to the cell suppresses this effect.

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.

Effect of TiO{sub 2} thickness on nanocomposited aligned ZnO nanorod/TiO{sub 2} for dye-sensitized solar cells

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

Saurdi, I., E-mail: saurdy788@gmail.com; Ishak, A.; UiTM Sarawak Kampus Kota Samarahan Jalan Meranek, Sarawak

2016-07-06

The TiO{sub 2} films were deposited on glass substrate at different thicknesses with different deposition frequencies (1, 2, 3 and 4 times) using spin coating technique and their structural properties were investigated. Subsequently, the nanocomposited aligned ZnO nanorods and TiO{sub 2} were formed by deposited the TiO{sub 2} on top of aligned ZnO Nanorod on ITO-coated glass at different thicknesses using the same method of TiO{sub 2} deposited on glass substrate. The nanocomposited aligned ZnO nanorod/TiO{sub 2} were coated with different thicknesses of 900µm, 1815µm, 2710µm, 3620µm and ZnO without TiO{sub 2}. The dye-sensitized solar cells were fabricated from themore » nanocomposited aligned ZnO nanorod/TiO{sub 2} with thickness of 900µm, 1815µm, 2710µm and 3620µm and ZnO without TiO{sub 2} and their photovoltaic properties of the DSSCs were investigated. From the solar simulator measurement the solar energy conversion efficiency (η) of 2.543% under AM 1.5 was obtained for the ZnO nanorod/TiO{sub 2} photoanode-2710µm Dye-Sensitized solar cell.« less

Anisotropic Dye Adsorption and Anhydrous Proton Conductivity in Smectic Liquid Crystal Networks: The Role of Cross-Link Density, Order, and Orientation.

PubMed

Liang, Ting; van Kuringen, Huub P C; Mulder, Dirk J; Tan, Shuai; Wu, Yong; Borneman, Zandrie; Nijmeijer, Kitty; Schenning, Albertus P H J

2017-10-11

In this work, the decisive role of rigidity, orientation, and order in the smectic liquid crystalline network on the anisotropic proton and adsorbent properties is reported. The rigidity in the hydrogen-bonded polymer network has been altered by changing the cross-link density, the order by using different mesophases (smectic, nematic, and isotropic phases), whereas the orientation of the mesogens was controlled by alignment layers. Adding more cross-linkers improved the integrity of the polymer films. For the proton conduction, an optimum was found in the amount of cross-linker and the smectic organization results in the highest anhydrous proton conduction. The polymer films show anisotropic proton conductivity with a 54 times higher conductivity in the direction perpendicular to the molecular director. After a base treatment of the smectic liquid crystalline network, a nanoporous polymer film is obtained that also shows anisotropic adsorption of dye molecules and again straight smectic pores are favored over disordered pores in nematic and isotropic networks. The highly cross-linked films show size-selective adsorption of dyes. Low cross-linked materials do not show this difference due to swelling, which decreases the order and creates openings in the two-dimensional polymer layers. The latter is, however, beneficial for fast adsorption kinetics.

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.

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.

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

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

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 Efficiency Dye-sensitized Solar Cells Constructed with Composites of TiO2 and the Hot-bubbling Synthesized Ultra-Small SnO2 Nanocrystals.

PubMed

Mao, Xiaoli; Zhou, Ru; Zhang, Shouwei; Ding, Liping; Wan, Lei; Qin, Shengxian; Chen, Zhesheng; Xu, Jinzhang; Miao, Shiding

2016-01-13

An efficient photo-anode for the dye-sensitized solar cells (DSSCs) should have features of high loading of dye molecules, favorable band alignments and good efficiency in electron transport. Herein, the 3.4 nm-sized SnO2 nanocrystals (NCs) of high crystallinity, synthesized via the hot-bubbling method, were incorporated with the commercial TiO2 (P25) particles to fabricate the photo-anodes. The optimal percentage of the doped SnO2 NCs was found at ~7.5% (SnO2/TiO2, w/w), and the fabricated DSSC delivers a power conversion efficiency up to 6.7%, which is 1.52 times of the P25 based DSSCs. The ultra-small SnO2 NCs offer three benefits, (1) the incorporation of SnO2 NCs enlarges surface areas of the photo-anode films, and higher dye-loading amounts were achieved; (2) the high charge mobility provided by SnO2 was confirmed to accelerate the electron transport, and the photo-electron recombination was suppressed by the highly-crystallized NCs; (3) the conduction band minimum (CBM) of the SnO2 NCs was uplifted due to the quantum size effects, and this was found to alleviate the decrement in the open-circuit voltage. This work highlights great contributions of the SnO2 NCs to the improvement of the photovoltaic performances in the DSSCs.

High Efficiency Dye-sensitized Solar Cells Constructed with Composites of TiO2 and the Hot-bubbling Synthesized Ultra-Small SnO2 Nanocrystals

PubMed Central

Mao, Xiaoli; Zhou, Ru; Zhang, Shouwei; Ding, Liping; Wan, Lei; Qin, Shengxian; Chen, Zhesheng; Xu, Jinzhang; Miao, Shiding

2016-01-01

An efficient photo-anode for the dye-sensitized solar cells (DSSCs) should have features of high loading of dye molecules, favorable band alignments and good efficiency in electron transport. Herein, the 3.4 nm-sized SnO2 nanocrystals (NCs) of high crystallinity, synthesized via the hot-bubbling method, were incorporated with the commercial TiO2 (P25) particles to fabricate the photo-anodes. The optimal percentage of the doped SnO2 NCs was found at ~7.5% (SnO2/TiO2, w/w), and the fabricated DSSC delivers a power conversion efficiency up to 6.7%, which is 1.52 times of the P25 based DSSCs. The ultra-small SnO2 NCs offer three benefits, (1) the incorporation of SnO2 NCs enlarges surface areas of the photo-anode films, and higher dye-loading amounts were achieved; (2) the high charge mobility provided by SnO2 was confirmed to accelerate the electron transport, and the photo-electron recombination was suppressed by the highly-crystallized NCs; (3) the conduction band minimum (CBM) of the SnO2 NCs was uplifted due to the quantum size effects, and this was found to alleviate the decrement in the open-circuit voltage. This work highlights great contributions of the SnO2 NCs to the improvement of the photovoltaic performances in the DSSCs. PMID:26758941

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

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.

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.

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.

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.

Product kinetic and internal energy distributions via velocity-aligned Doppler spectroscopy: Technical report, May 1985-January 1987

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

Wittig, C.

1987-01-01

We developed a method of sub-Doppler resolution spectroscopy that is useful for determining kinetic energy distributions. With 'conventional' Doppler spectroscopy, it is almost impossible to obtain an accurate distribution from a line profile, even with the highest resolution, except when the distribution is quite simple (e.g., a delta function). This is due to the lineshape deriving from velocity components along the wave-vector of the probe radiation, k/sub probe/. However, by choosing only those species whose velocities are essentially parallel (or antiparallel) to k/sub probe/, this handicap is overcome. Here, one obtains the kinetic energy distribution along k/sub probe/, and themore » resolution is limited only by our ability to reject species with velocity components perpendicular to k/sub probe/. This rejection is done by spatial and temporal discrimination, using counterpropagating, overlapped, pulsed photolysis and probe sources. At long delays, molecules are detected which are aligned with k/sub probe/. We call the method velocity-aligned Doppler spectroscopy (VADS). We have perused several cases involving photodissociation of small molecules, in each case detecting H-atoms using sequential 2-photon ionization via Lyman-..cap alpha... We discern structure in the kinetic energy distribution which is attributed to internal excitation of the 'other' fragment, and resolution is limited by the dye laser bandwidth. In the case of HBr, we resolve the Br spin-orbit states, and with H/sub 2/S, we resolve the SH vibrational levels. 38 refs., 7 figs.« less

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.

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.

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.

Stable azodye photo-alignment layer for liquid crystal devices achieved by "turning off" dye photosensitivity

NASA Astrophysics Data System (ADS)

McGinty, C.; Finnemeyer, V.; Reich, R.; Clark, H.; Berry, S.; Bos, P.

2017-11-01

We have previously proposed a low cost, versatile process for stabilizing azodye photo-alignment layers for liquid crystal devices by utilizing a surface localized reactive mesogen (RM) layer. The RM is applied by dissolving the monomer in a liquid crystal material prior to filling the cell. In this paper, we show the significant effect of azodye layer thickness on the long term stability of these alignment layers when exposed to polarized light. We demonstrate, surprisingly, that thin azodye layers (˜3 nm) provide improved stability over thicker (˜40 nm) layers. Using this process, we show cells which have been stable to exposure with polarized light through one month. Additionally, we demonstrate the use of a photo-alignment layer to align the liquid crystals that afterwards can be rendered insensitive to polarized light. This was accomplished by using the process described above with the additional step of eliminating the photosensitivity of the azodye layer through photo-bleaching; the result is an RM alignment layer that will be stable when exposed to polarized light in the dye absorption band.

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.

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.

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

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.

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.

Adiabatic Field-Free Alignment of Asymmetric Top Molecules with an Optical Centrifuge.

PubMed

Korobenko, A; Milner, V

2016-05-06

We use an optical centrifuge to align asymmetric top SO_{2} molecules by adiabatically spinning their most polarizable O-O axis. The effective centrifugal potential in the rotating frame confines the sulfur atoms to the plane of the laser-induced rotation, leading to the planar molecular alignment that persists after the molecules are released from the centrifuge. The periodic appearance of the full three-dimensional alignment, typically observed only with linear and symmetric top molecules, is also detected. Together with strong in-plane centrifugal forces, which bend the molecules by up to 10 deg, permanent field-free alignment offers new ways of controlling molecules with laser light.

The influence of the distance between the donor-acceptor groups of polymethine dyes on their photovoltaic properties

NASA Astrophysics Data System (ADS)

Seliverstova, E.; Ibrayev, N.

2018-01-01

Spectral-luminescent and photovoltaic properties of polymethine dyes of various structures are studied. It is shown that an increase in the length of the methylene chain between the active chromophores leads to a red-wave shift of the absorption and fluorescence spectra. Significant changes in the absorptivity and lifetime of fluorescence do not occur in this case. The best photovoltaic parameters have cells sensitized with shorter dye molecules. It is shown, that for a longer dye the resistance associated with electron recombination on the TiO2/electrolyte surface is much higher than the electron transfer resistance in the semiconductor, which reduces the efficiency of electron transfer in the solar cell, sensitized with longer dye molecules.

Role of step edges on the structure formation of α-6T on Ag(441)

NASA Astrophysics Data System (ADS)

Wagner, Thorsten; Fritz, Daniel Roman; Rudolfová, Zdena; Zeppenfeld, Peter

2018-01-01

Controlling the orientation of organic molecules on surfaces is important in order to tune the physical properties of the organic thin films and, thereby, increase the performance of organic thin film devices. Here, we present a scanning tunneling microscopy (STM) and photoelectron emission microscopy (PEEM) study of the deposition of the organic dye pigment α-sexithiophene (α-6T) on the vicinal Ag(441) surface. In the presence of the steps on the Ag(441) surface, the α-6T molecules exclusively align parallel to the step edges oriented along the [1 1 bar0]-direction of the substrate. The STM results further reveal that the adsorption of the α-6T molecules is accompanied by various restructuring of the substrate surface: Initially, the molecules prefer the Ag(551) building blocks of the Ag(441) surface. The Ag(551) termination of the terraces is then changed to a predominately Ag(331) one upon completion of the first α-6T monolayer. When closing the two layer thick wetting layer, the original ratio of Ag(331) and Ag(551) building blocks ( ≈ 1:1) is recovered, but a phase separation into microfacets, which are composed either of Ag(331) or of Ag(551) building blocks, is found.

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

Dye anchored ZnO nanoparticles: The positive and negative photoluminescence quenching effects

NASA Astrophysics Data System (ADS)

Ganesh, T.; Kim, Jong Hoon; Yoon, Seog Joon; Lee, Sangjin; Lee, Wonjoo; Mane, Rajaram S.; Han, Jin Wook; Han, Sung-Hwan

2009-10-01

The positive and negative photoluminescence quenching effects in dye [BCMoxo and BCtCM (curcumin-derived molecules)] anchored ZnO nanoparticles (NPs) are investigated using the optical and electronic properties. The photoluminescence, band gap (BCMoxo, 2.2 eV; BCtCM, 2.3 eV), and wettability studies confirm an optical quenching, well-matched electronic structure and relative hydrophobic nature, respectively, in the presence of dicarboxylic anchor groups (BCtCM) on ZnO NPs in contrast to that of keto groups (BCMoxo). Systematic change in UV-visible absorption band edge is noticeable for the BCtCM and BCMoxo-anchored ZnO NPs. The atomic absorption spectroscopy and inductively coupled-mass-spectroscopy analysis quantitatively verifies the amount of BCtCM dye molecules present on ZnO NPs surface area about three times higher than that of BCMoxo dye molecule without anchor groups.

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.

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.

Dissipation dynamics of field-free molecular alignment for symmetric-top molecules: Ethane (C2H6)

NASA Astrophysics Data System (ADS)

Zhang, H.; Billard, F.; Yu, X.; Faucher, O.; Lavorel, B.

2018-03-01

The field-free molecular alignment of symmetric-top molecules, ethane, induced by intense non-resonant linearly polarized femtosecond laser pulses is investigated experimentally in the presence of collisional relaxation. The dissipation dynamics of field-free molecular alignment are measured by the balanced detection of ultrafast molecular birefringence of ethane gas samples at high pressures. By separating the molecular alignment into the permanent alignment and the transient alignment, the decay time-constants of both components are quantified at the same pressure. It is observed that the permanent alignment always decays slower compared to the transient alignment within the measured pressure range. This demonstrates that the propensity of molecules to conserve the orientation of angular momentum during collisions, previously observed for linear species, is also applicable to symmetric-top molecules. The results of this work provide valuable information for further theoretical understanding of collisional relaxation within nonlinear polyatomic molecules, which are expected to present interesting and nontrivial features due to an extra rotational degree of freedom.

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

Photoaligning and photopatterning technology: applications in displays and photonics

NASA Astrophysics Data System (ADS)

Chigrinov, Vladimir

2016-03-01

The advantages of LC photoalignment technology in comparison with common "rubbing" alignment methods tend to the continuation of the research in this field. Almost all the criteria of perfect LC alignment are met in case of azo-dye layers. Nowadays azo-dye alignment materials can be already used in LCD manufacturing, e.g. for the alignment of monomers in LCP films for new generations of photonics and optics devices. Recently the new application of photoaligned technology for the tunable LC lenses with a variable focal distance was proposed. New optically rewritable (ORW) liquid crystal display and photonics devices with a light controllable structure may include LC E-paper screens, LC lenses with a variable focal distance etc. Fast ferroelectric liquid crystal devices (FLCD) are achieved through the application of nano-scale photo aligning (PA) layers in FLC cells. The novel photoaligned FLC devices may include field sequential color (FSC) FLC with a high resolution, high brightness, low power consumption and extended color gamut to be used for PCs, PDAs, switchable goggles, and new generation of switchable 2D/3D LCD TVs, as well as photonics elements.

Local-global alignment for finding 3D similarities in protein structures

DOEpatents

Zemla, Adam T [Brentwood, CA

2011-09-20

A method of finding 3D similarities in protein structures of a first molecule and a second molecule. The method comprises providing preselected information regarding the first molecule and the second molecule. Comparing the first molecule and the second molecule using Longest Continuous Segments (LCS) analysis. Comparing the first molecule and the second molecule using Global Distance Test (GDT) analysis. Comparing the first molecule and the second molecule using Local Global Alignment Scoring function (LGA_S) analysis. Verifying constructed alignment and repeating the steps to find the regions of 3D similarities in protein structures.

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.

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.

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...

Construction of a Visible Diode Laser Source for Free Radical Photochemistry and Spectroscopy Experiments

NASA Technical Reports Server (NTRS)

Newman, Bronjelyn; Halpern, Joshua B.

1997-01-01

Tunable diode lasers are reliable sources of narrow-band light and comparatively cheap. Optical feedback simplifies frequency tuning of the laser diodes. We are building an inexpensive diode laser system incorporating optical feedback from a diffraction grating. The external optical cavity can be used with lasers that emit between 2 and 100 mW, and will also work if they are pulsed, although this will significantly degrade the bandwidth. The diode laser output power and bandwidth are comparable to CW dye lasers used in kinetics and dynamics experiments. However, their cost and maintenance will be much less as will alignment time. We intend to use the diode lasers to investigate CN and C2 kinetics as well as to study dissociation dynamics of atmospherically important molecules.

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.

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.

Electrically switchable photonic liquid crystal devices for routing of a polarized light wave

NASA Astrophysics Data System (ADS)

Rushnova, Irina I.; Melnikova, Elena A.; Tolstik, Alexei L.; Muravsky, Alexander A.

2018-04-01

The new mode of LC alignment based on photoalignment AtA-2 azo dye where the refractive interface between orthogonal orientations of the LC director exists without voltage and disappeared or changed with critical voltage has been proposed. The technology to fabricate electrically controlled liquid crystal elements for spatial separation and switching of linearly polarized light beams on the basis of the total internal reflection effect has been significantly improved. Its distinctive feature is the application of a composite alignment material comprising two sublayers of Nylon-6 and AtA-2 photoalignment azo dye offering patterned liquid crystal director orientation with high alignment quality value q = 0 . 998. The fabricated electrically controlled spatially structured liquid crystal devices enable implementation of propagation directions separation for orthogonally polarized light beams and their switching with minimal crosstalk.

Highly Enhanced Gas Adsorption Properties in Vertically Aligned MoS2 Layers.

PubMed

Cho, Soo-Yeon; Kim, Seon Joon; Lee, Youhan; Kim, Jong-Seon; Jung, Woo-Bin; Yoo, Hae-Wook; Kim, Jihan; Jung, Hee-Tae

2015-09-22

In this work, we demonstrate that gas adsorption is significantly higher in edge sites of vertically aligned MoS2 compared to that of the conventional basal plane exposed MoS2 films. To compare the effect of the alignment of MoS2 on the gas adsorption properties, we synthesized three distinct MoS2 films with different alignment directions ((1) horizontally aligned MoS2 (basal plane exposed), (2) mixture of horizontally aligned MoS2 and vertically aligned layers (basal and edge exposed), and (3) vertically aligned MoS2 (edge exposed)) by using rapid sulfurization method of CVD process. Vertically aligned MoS2 film shows about 5-fold enhanced sensitivity to NO2 gas molecules compared to horizontally aligned MoS2 film. Vertically aligned MoS2 has superior resistance variation compared to horizontally aligned MoS2 even with same surface area exposed to identical concentration of gas molecules. We found that electrical response to target gas molecules correlates directly with the density of the exposed edge sites of MoS2 due to high adsorption of gas molecules onto edge sites of vertically aligned MoS2. Density functional theory (DFT) calculations corroborate the experimental results as stronger NO2 binding energies are computed for multiple configurations near the edge sites of MoS2, which verifies that electrical response to target gas molecules (NO2) correlates directly with the density of the exposed edge sites of MoS2 due to high adsorption of gas molecules onto edge sites of vertically aligned MoS2. We believe that this observation extends to other 2D TMD materials as well as MoS2 and can be applied to significantly enhance the gas sensor performance in these materials.

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

Ultra-fast microwave-assisted hydrothermal synthesis of long vertically aligned ZnO nanowires for dye-sensitized solar cell application.

PubMed

Mahpeykar, S M; Koohsorkhi, J; Ghafoori-Fard, H

2012-04-27

Long vertically aligned ZnO nanowire arrays were synthesized using an ultra-fast microwave-assisted hydrothermal process. Using this method, we were able to grow ZnO nanowire arrays at an average growth rate as high as 200 nm min(-1) for maximum microwave power level. This method does not suffer from the growth stoppage problem at long growth times that, according to our investigations, a normal microwave-assisted hydrothermal method suffers from. Longitudinal growth of the nanowire arrays was investigated as a function of microwave power level and growth time using cross-sectional FESEM images of the grown arrays. Effect of seed layer on the alignment of nanowires was also studied. X-ray diffraction analysis confirmed c-axis orientation and single-phase wurtzite structure of the nanowires. J-V curves of the fabricated ZnO nanowire-based mercurochrome-sensitized solar cells indicated that the short-circuit current density is increased with increasing the length of the nanowire array. According to the UV-vis spectra of the dyes detached from the cells, these increments were mainly attributed to the enlarged internal surface area and therefore dye loading enhancement in the lengthened nanowire arrays.

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.

High-harmonic spectroscopy of aligned molecules

NASA Astrophysics Data System (ADS)

Yun, Hyeok; Yun, Sang Jae; Lee, Gae Hwang; Nam, Chang Hee

2017-01-01

High harmonics emitted from aligned molecules driven by intense femtosecond laser pulses provide the opportunity to explore the structural information of molecules. The field-free molecular alignment technique is an expedient tool for investigating the structural characteristics of linear molecules. The underlying physics of field-free alignment, showing the characteristic revival structure specific to molecular species, is clearly explained from the quantum-phase analysis of molecular rotational states. The anisotropic nature of molecules is shown from the harmonic polarization measurement performed with spatial interferometry. The multi-orbital characteristics of molecules are investigated using high-harmonic spectroscopy, applied to molecules of N2 and CO2. In the latter case the two-dimensional high-harmonic spectroscopy, implemented using a two-color laser field, is applied to distinguish harmonics from different orbitals. Molecular high-harmonic spectroscopy will open a new route to investigate ultrafast dynamics of molecules.

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.

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.

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.

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.

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.

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.

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.

Charge transfer at organic-inorganic interfaces—Indoline layers on semiconductor substrates

NASA Astrophysics Data System (ADS)

Meyenburg, I.; Falgenhauer, J.; Rosemann, N. W.; Chatterjee, S.; Schlettwein, D.; Heimbrodt, W.

2016-12-01

We studied the electron transfer from excitons in adsorbed indoline dye layers across the organic-inorganic interface. The hybrids consist of indoline derivatives on the one hand and different inorganic substrates (TiO2, ZnO, SiO2(0001), fused silica) on the other. We reveal the electron transfer times from excitons in dye layers to the organic-inorganic interface by analyzing the photoluminescence transients of the dye layers after femtosecond excitation and applying kinetic model calculations. A correlation between the transfer times and four parameters have been found: (i) the number of anchoring groups, (ii) the distance between the dye and the organic-inorganic interface, which was varied by the alkyl-chain lengths between the carboxylate anchoring group and the dye, (iii) the thickness of the adsorbed dye layer, and (iv) the level alignment between the excited dye ( π* -level) and the conduction band minimum of the inorganic semiconductor.

Master dye laser oscillator including a specific grating assembly for use therein

DOEpatents

Davin, James M.

1992-01-01

A dye laser oscillator for producing a tuned dye beam is disclosed herein and includes, among other components, a beam output coupling assembly, a dye cell assembly, a beam expander assembly, an etalon assembly, and a grating assembly. Each of three assemblies is vertically supported from a horizontal base so as to be readily removable from the base without interference from or interfering with the other assemblies. The particular grating assembly disclosed is specifically designed for proper optical alignment with the intended path of the dye beam to be produced and for accurate pivotal movement relative to the beam path in order to function as a coarse tuning mechanism in the production of the ultimately tuned beam.

Master dye laser oscillator including a specific grating assembly for use therein

DOEpatents

Davin, J.M.

1992-09-01

A dye laser oscillator for producing a tuned dye beam is disclosed herein and includes, among other components, a beam output coupling assembly, a dye cell assembly, a beam expander assembly, an etalon assembly, and a grating assembly. Each of three assemblies is vertically supported from a horizontal base so as to be readily removable from the base without interference from or interfering with the other assemblies. The particular grating assembly disclosed is specifically designed for proper optical alignment with the intended path of the dye beam to be produced and for accurate pivotal movement relative to the beam path in order to function as a coarse tuning mechanism in the production of the ultimately tuned beam. 5 figs.

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.

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

Electronic structure measurements of metal-organic solar cell dyes using x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Johnson, Phillip S.

The focus of this thesis is twofold: to report the results of X-ray absorption studies of metal-organic dye molecules for dye-sensitized solar cells and to provide a basic training manual on X-ray absorption spectroscopy techniques and data analysis. The purpose of our research on solar cell dyes is to work toward an understanding of the factors influencing the electronic structure of the dye: the choice of the metal, its oxidation state, ligands, and cage structure. First we study the effect of replacing Ru in several common dye structures by Fe. First-principles calculations and X-ray absorption spectroscopy at the C 1s and N 1s edges are combined to investigate transition metal dyes in octahedral and square planar N cages. Octahedral molecules are found to have a downward shift in the N 1s-to-pi* transition energy and an upward shift in C 1s-to-pi* transition energy when Ru is replaced by Fe, explained by an extra transfer of negative charge from Fe to the N ligands compared to Ru. For the square planar molecules, the behavior is more complex because of the influence of axial ligands and oxidation state. Next the crystal field parameters for a series of phthalocyanine and porphyrins dyes are systematically determined using density functional calculations and atomic multiplet calculations with polarization-dependent X-ray absorption spectra. The polarization dependence of the spectra provides information on orbital symmetries which ensures the determination of the crystal field parameters is unique. A uniform downward scaling of the calculated crystal field parameters by 5-30% is found to be necessary to best fit the spectra. This work is a part of the ongoing effort to design and test new solar cell dyes. Replacing the rare metal Ru with abundant metals like Fe would be a significant advance for dye-sensitized solar cells. Understanding the effects of changing the metal centers in these dyes in terms of optical absorption, charge transfer, and electronic structure enables the systematic design of new dyes using less expensive materials.

Intensity calibration of a laser scanning confocal microscope based on concentrated dyes.

PubMed

Model, Michael A; Blank, James L

2006-10-01

To find water-soluble fluorescent dyes with absorption in various regions of the spectrum and investigate their utility as standards for laser scanning confocal microscopy. Several dyes were found to have characteristics required for fluorescence microscopy standards. The intensity of biological fluorescent specimens was measured against the emission of concentrated dyes. Results using different optics and different microscopes were compared. Slides based on concentrated dyes can be prepared in a highly reproducible manner and are stable under laser scanning. Normalized fluorescence of biological specimens remains consistent with different objective lenses and is tolerant to some mismatch in optical filters or imperfect pinhole alignment. Careful choice of scanning parameters is necessary to ensure linearity of intensity measurements. Concentrated dyes provide a robust and inexpensive intensity standard that can be used in basic research or clinical studies.

Fast novel nonlinear optical NLC system with local response

NASA Astrophysics Data System (ADS)

Iljin, Andrey; Residori, Stefania; Bortolozzo, Umberto

2017-06-01

Nonlinear optical performance of a novel liquid crystalline (LC) cell has been studied in two-wave mixing experiments revealing high diffraction efficiency within extremely wide intensity range, fast recording times and spatial resolution. Photo-induced modulation of the LC order parameter resulting from trans-cis isomerisation of dye molecules causes consequent changes of refractive indices of the medium (Light-Induced Order Modification, LIOM-mechanism) and is proved to be the main mechanism of optical nonlinearity. The proposed arrangement of the electric-field-stabilised homeotropic alignment hinders the LC director reorientation, prevents appearance of surface effects and ensures the optical cell quality. The LIOM-type nonlinearity, characterised with the substantially local nonlinear optical response, could also be extended for the recording of arbitrary phase profiles as requested in several applications for light-beam manipulation, recording of dynamic volume holograms and photonic lattices.

Dichroic Liquid Crystal Displays

NASA Astrophysics Data System (ADS)

Bahadur, Birendra

The following sections are included: * INTRODUCTION * DICHROIC DYES * Chemical Structure * Chemical and Photochemical Stability * THEORETICAL MODELLING * DEFECTS CAUSED BY PROLONGED LIGHT IRRADIATION * CHEMICAL STRUCTURE AND PHOTOSTABILITY * OTHER PARAMETERS AFFECTING PHOTOSTABILITY * CELL PREPARATION * DICHROIC PARAMETERS AND THEIR MEASUREMENTS * Order Parameter and Dichroic Ratio Of Dyes * Absorbance, Order Parameter and Dichroic Ratio Measurements * IMPACT OF DYE STRUCTURE AND LIQUID CRYSTAL HOST ON PHYSICAL PROPERTIES OF A DICHROIC MIXTURE * Order Parameter and Dichroic Ratio * EFFECT OF LENGTH OF DICHROIC DYES ON THE ORDER PARAMETER * EFFECT OF THE BREADTH OF DYE ON THE ORDER PARAMETER * EFFECT OF THE HOST ON THE ORDER PARAMETER * TEMPERATURE VARIATION OF THE ORDER PARAMETER OF DYES IN A LIQUID CRYSTAL HOST * IMPACT OF DYE CONCENTRATION ON THE ORDER PARAMETER * Temperature Range * Viscosity * Dielectric Constant and Anisotropy * Refractive Indices and Birefringence * solubility43,153-156 * Absorption Wavelength and Auxochromic Groups * Molecular Engineering of Dichroic Dyes * OPTICAL, ELECTRO-OPTICAL AND LIFE PARAMETERS * Colour And CIE Colour space120,160-166 * CIE 1931 COLOUR SPACE * CIE 1976 CHROMATICITY DIAGRAM * CIE UNIFORM COLOUR SPACES & COLOUR DIFFERENCE FORMULAE120,160-166 * Electro-Optical Parameters120 * LUMINANCE * CONTRAST AND CONTRAST RATIO * SWITCHING SPEED * Life Parameters and Failure Modes * DICHROIC MIXTURE FORMULATION * Monochrome Mixture * Black Mixture * ACHROMATIC BLACK MIXTURE FOR HEILMEIER DISPLAYS * Effect of Illuminant on Display Colour * Colour of the Field-On State * Effect of Dye Linewidth * Optimum Centroid Wavelengths * Effect of Dye Concentration * Mixture Formulation Using More Than Three Dyes * ACHROMATIC MIXTURE FOR WHITE-TAYLOR TYPE DISPLAYS * HEILMEIER DISPLAYS * Theoretical Modelling * Threshold Characteristic * Effects of Dye Concentration on Electro-optical Parameters * Effect of Cholesteric Doping * Effect of Alignment * Effect of Thickness * Impact of Order Parameter * Impact of the Host * Impact of Polarizer * Colour Applications * Multiplexing * QUARTER WAVE PLATE DICHROIC DISPLAYS * Operational Principle and Display Configuration11-13 * Electro-Optical Performance * DYE-DOPED TN DISPLAYS * Threshold Characteristic, Contrast Ratio and Switching Speed * PHASE CHANGE EFFECT DICHROIC LCDs * Theoretical Background * Threshold Characteristic and Molecular Orientation * MOLECULAR ORIENTATION DURING FIELD-INDUCED PHASE TRANSITION WITH HOMOGENEOUS WALL ALIGNMENT * MOLECULAR ORIENTATION DURING FIELD-INDUCED PHASE TRANSITION WITH HOMEOTROPIC WALL ALIGNMENT * Contrast Ratio, Transmission, Brightness and Switching Speed3,7,10,198-214 * Memory or Reminiscent Contrast * Electro-optical Performance vs. Temperature * Multiplexing Phase Change Dichroic LCDs * DOUBLE CELL DICHROIC LCDs3,9,14-17,232-234 * Double Cell Nematic Dichroic LCD3,8,9,14,15,233 * Double Cell One Pitch Cholesteric LCD16,17 * Double Cell Phase Change Dichroic LCD214,232 * POSITIVE MODE DICHROIC LCDS3,8,9 * Positive Mode Heilmeier Cells3,8,9,43,77,78,235-238 * USING PLEOCHROIC DYES3,8,9,43,235-238 * USING NEGATIVE DICHROIC DYES3,8,9,63,77,78156 * DUAL FREQUENCY ADDRESSED DICHROIC DISPLAYS75,238 * Positive Mode Dichroic LCDs Using λ/4 Plate * Positive Mode Double Cell Dichroic LCD * Positive Mode Dichroic LCDs Using Special Electrode patterns7,8,239-241 * Positive Mode Phase Change Dichroic LCDs3,8,9,230,243-248 * Dichroic LCDs Using an Admixture of Pleochroic and Negative Dichroic Dyes78,118 * SUPERTWIST DICHROIC EFFECT (SDE) DISPLAYS21-23 * FERROELECTRIC DICHROIC LCDs24-27 * Devices Using A Single Polarizer * Devices Using No Polarizer24-27 * POLYMER DISPERSED DICHROIC LCDs28-30,252-259 * DICHROIC POLYMER LIQUID CRYSTAL DISPLAYS * Heilmeier Type Displays * Guest-Host Cell Using an Admixture Of L.C. Polymer and Low Molecular Weight Liquid Crysta As Host * Polymeric Ferroelectric Dichroic LCDs * SMECTIC A DICHROIC LCDs * Laser Addressed Dichroic SA Displays * Thermally and Electrically Addressed Dichroic SA Displays * FLUORESCENT DICHROIC LCDs * ACKNOWLEDGEMENTS * REFERENCES

Fabrication and mechanical behavior of dye-doped polymer optical fiber

NASA Astrophysics Data System (ADS)

Jiang, Changhong; Kuzyk, Mark G.; Ding, Jow-Lian; Johns, William E.; Welker, David J.

2002-07-01

The purpose of this article is to study the materials physics behind dye-doped polymethyl metharcylate (PMMA) that is important for the optical fiber drawing process. We report effects of the fabrication process on the mechanical properties of the final fiber. The qualitative degree of polymer chain alignment is found to increase with the drawing force, which in turn decreases with the drawing temperature and increases with the drawing ratio. The chain alignment relaxes when the fibers are annealed at 95 degC with a commensurate decrease in fiber length and increase in diameter. The annealed fiber has higher ductility but lower strength than the unannealed fiber. Both the yield and tensile strengths are dependent on the strain rate. The relationship between tensile strength, sigmab, and fiber diameter, d, is found empirically to be sigmab[is proportional to]d-0.5. The yield strength appears to be less sensitive to the fiber diameter than the tensile strength. For PMMA doped with disperse red 1 azo dye, the yield strength, tensile strength, and Young's modulus peak at a dye concentration of 0.0094 wt %. These results are useful for designing polymer optical fibers with well-defined mechanical properties.

Plasmonic nanoparticles enhanced dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Xu, Qi; Liu, Fang; Meng, Weisi; Huang, Yidong

2013-12-01

Here we present investigations on utilizing two kinds of plasmonic nanoparticles (NPs) to enhance the efficiency of dye sensitized solar cells (DSCs). The Au@PVP NPs is proposed and present the specialty of adhesiveness to dye molecules, which could help to localize additional dye molecules near the plasmonic NPs, hence increasing the optical absorption consequently the power conversion efficiency (PCE) of the DSCs by 30% from 3.3% to 4.3%. Meanwhile, an irregular Au-Ag alloy popcorn-shaped NPs (popcorn NPs) with plenty of fine structures is also proposed and realized to enhance the light absorption of DSC. A pronounced absorption enhancement in a broadband wavelength range is observed due to the excitation of localized surface plasmon at different wavelengths. The PCE is enhanced by 32% from 5.94% to 7.85%.

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

Carbon nanofibers arrays: A novel tool for microdelivery of biomolecules to plants

DOE PAGES

Davern, Sandra M.; McKnight, Timothy E.; Kalluri, Udaya C.; ...

2016-04-27

Effective methods for delivering bioprobes into the cells of intact plants are essential for investigating diverse biological processes. Increasing research on trees, such as Populus spp., for bioenergy applications is driving the need for techniques that work well with tree species. This report introduces vertically aligned carbon nanofiber (VACNF) arrays as a new tool for microdelivery of labeled molecules to Populus leaf tissue and whole plants. We demonstrated that VACNFs penetrate the leaf surface to deliver sub-microliter quantities of solution containing fluorescent or radiolabeled molecules into Populus leaf cells. Importantly, VACNFs proved to be gentler than abrasion with carborundum, amore » common way to introduce material into leaves. Unlike carborundum, VACNFs did not disrupt cell or tissue integrity, nor did they induce production of hydrogen peroxide, a typical wound response. We show that femtomole to picomole quantities of labeled molecules (fluorescent dyes, small proteins and dextran), ranging from 0.5–500 kDa, can be introduced by VACNFs, and we demonstrate the use of the approach to track delivered probes from their site of introduction on the leaf to distal plant regions. VACNF arrays thus offer an attractive microdelivery method for the introduction of biomolecules and other probes into trees and potentially other types of plants.« less

Carbon nanofibers arrays: A novel tool for microdelivery of biomolecules to plants

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

Davern, Sandra M.; McKnight, Timothy E.; Kalluri, Udaya C.

Effective methods for delivering bioprobes into the cells of intact plants are essential for investigating diverse biological processes. Increasing research on trees, such as Populus spp., for bioenergy applications is driving the need for techniques that work well with tree species. This report introduces vertically aligned carbon nanofiber (VACNF) arrays as a new tool for microdelivery of labeled molecules to Populus leaf tissue and whole plants. We demonstrated that VACNFs penetrate the leaf surface to deliver sub-microliter quantities of solution containing fluorescent or radiolabeled molecules into Populus leaf cells. Importantly, VACNFs proved to be gentler than abrasion with carborundum, amore » common way to introduce material into leaves. Unlike carborundum, VACNFs did not disrupt cell or tissue integrity, nor did they induce production of hydrogen peroxide, a typical wound response. We show that femtomole to picomole quantities of labeled molecules (fluorescent dyes, small proteins and dextran), ranging from 0.5–500 kDa, can be introduced by VACNFs, and we demonstrate the use of the approach to track delivered probes from their site of introduction on the leaf to distal plant regions. VACNF arrays thus offer an attractive microdelivery method for the introduction of biomolecules and other probes into trees and potentially other types of plants.« less

Carbon Nanofiber Arrays: A Novel Tool for Microdelivery of Biomolecules to Plants

PubMed Central

Davern, Sandra M.; McKnight, Timothy E.; Morrell-Falvey, Jennifer L.; Shpak, Elena D.; Kalluri, Udaya C.; Jelenska, Joanna; Greenberg, Jean T.; Mirzadeh, Saed

2016-01-01

Effective methods for delivering bioprobes into the cells of intact plants are essential for investigating diverse biological processes. Increasing research on trees, such as Populus spp., for bioenergy applications is driving the need for techniques that work well with tree species. This report introduces vertically aligned carbon nanofiber (VACNF) arrays as a new tool for microdelivery of labeled molecules to Populus leaf tissue and whole plants. We demonstrated that VACNFs penetrate the leaf surface to deliver sub-microliter quantities of solution containing fluorescent or radiolabeled molecules into Populus leaf cells. Importantly, VACNFs proved to be gentler than abrasion with carborundum, a common way to introduce material into leaves. Unlike carborundum, VACNFs did not disrupt cell or tissue integrity, nor did they induce production of hydrogen peroxide, a typical wound response. We show that femtomole to picomole quantities of labeled molecules (fluorescent dyes, small proteins and dextran), ranging from 0.5–500 kDa, can be introduced by VACNFs, and we demonstrate the use of the approach to track delivered probes from their site of introduction on the leaf to distal plant regions. VACNF arrays thus offer an attractive microdelivery method for the introduction of biomolecules and other probes into trees and potentially other types of plants. PMID:27119338

Near-infrared absorption in symmetric squarylium and croconate dyes: a comparative study using symmetry-adapted cluster-configuration interaction methods.

PubMed

Prabhakar, Ch; Yesudas, K; Krishna Chaitanya, G; Sitha, Sanyasi; Bhanuprakash, K; Rao, V Jayathirtha

2005-09-29

Symmetric croconate (CR) and squarylium dyes (SQ) are well-known near-infrared (NIR) dyes and, in general, are considered to be donor-acceptor-donor type molecules. It is established in the literature that CR dyes absorb in a longer wavelength region than the corresponding SQ dyes. This has been attributed to the CR ring being a better acceptor than the SQ ring. Thus increasing the donor capacity should lead to a bathochromic shift in both SQ and CR. On the other hand, some experiments reported in the literature have revealed that increasing the conjugation in the donor part of the SQ molecule leads first to red shift, which upon a further increase of the conjugation changes to a blue shift. Hence, to understand the role of the central ring and the substitutions in the absorption of these dyes, we carried out high-level symmetry-adapted cluster-configuration interaction (SAC-CI) calculations of some substituted SQ and CR dyes and compare the absorption energy with the existing experimental data. We found that there is very good agreement. We also carried out SAC-CI calculations of some smaller model molecules, which contain the main oxyallyl substructure. We varied the geometry (angle) of the oxyallyl subgroup and the substitution in these model molecules to establish a correlation with the bathochromic shift. We found that the charge transfer is very small and does not play the key role in the red shift, but on the other hand, the perturbation of the HOMO-LUMO gap (HLG) from both the geometry and substitution seems to be responsible for this shift. We suggest as a design principle that increasing the donor capacity of the groups may not help in the red shift, but introducing groups which perturb the HLG and decrease it without changing the MO character should lead to a larger bathochromic shift.

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.

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.

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

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.

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.

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

3D flexible alignment using 2D maximum common substructure: dependence of prediction accuracy on target-reference chemical similarity.

PubMed

Kawabata, Takeshi; Nakamura, Haruki

2014-07-28

A protein-bound conformation of a target molecule can be predicted by aligning the target molecule on the reference molecule obtained from the 3D structure of the compound-protein complex. This strategy is called "similarity-based docking". For this purpose, we develop the flexible alignment program fkcombu, which aligns the target molecule based on atomic correspondences with the reference molecule. The correspondences are obtained by the maximum common substructure (MCS) of 2D chemical structures, using our program kcombu. The prediction performance was evaluated using many target-reference pairs of superimposed ligand 3D structures on the same protein in the PDB, with different ranges of chemical similarity. The details of atomic correspondence largely affected the prediction success. We found that topologically constrained disconnected MCS (TD-MCS) with the simple element-based atomic classification provides the best prediction. The crashing potential energy with the receptor protein improved the performance. We also found that the RMSD between the predicted and correct target conformations significantly correlates with the chemical similarities between target-reference molecules. Generally speaking, if the reference and target compounds have more than 70% chemical similarity, then the average RMSD of 3D conformations is <2.0 Å. We compared the performance with a rigid-body molecular alignment program based on volume-overlap scores (ShaEP). Our MCS-based flexible alignment program performed better than the rigid-body alignment program, especially when the target and reference molecules were sufficiently similar.

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.

Tilted Orientation of Photochromic Dyes with Guest-Host Effect of Liquid Crystalline Polymer Matrix for Electrical UV Sensing

PubMed Central

Ranjkesh, Amid; Park, Min-Kyu; Park, Do Hyuk; Park, Ji-Sub; Choi, Jun-Chan; Kim, Sung-Hoon; Kim, Hak-Rin

2015-01-01

We propose a highly oriented photochromic dye film for an ultraviolet (UV)-sensing layer, where spirooxazine (SO) derivatives are aligned with the liquid crystalline UV-curable reactive mesogens (RM) using a guest-host effect. For effective electrical UV sensing with a simple metal-insulator-metal structure, our results show that the UV-induced switchable dipole moment amount of the SO derivatives is high; however, their tilting orientation should be controlled. Compared to the dielectric layer with the nearly planar SO dye orientation, the photochromic dielectric layer with the moderately tilted dye orientation shows more than seven times higher the UV-induced capacitance variation. PMID:26729116

Adsorption Properties of p -Methyl Red Monomeric-to-Pentameric Dye Aggregates on Anatase (101) Titania Surfaces: First-Principles Calculations of Dye/TiO 2 Photoanode Interfaces for Dye-Sensitized Solar Cells

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

Zhang, Lei; Cole, Jacqueline M.

2014-08-29

The optical and electronic properties of dye aggregates of p-methyl red on a TiO2 anatase (101) surface were modeled as a function of aggregation order (monomer to pentameric dye) via first principles calculations. A progressive red-shifting and intensity increase toward the visible region in UV/vis absorption spectra is observed from monomeric-to-tetrameric dyes, with each molecule in a given aggregate binding to one of the four possible TiO2 (101) adsorption sites. The pentamer exhibits a blue-shifted peak wave- length in the UV/vis absorption spectra and less absorption intensity in the visible region in comparison; a corresponding manifestation of H-aggregation occurs sincemore » one of these five molecules cannot occupy an adsorption site. This finding is consistent with experiment. Calculated density of states (DOS) and partial DOS spectra reveal similar dye…TiO2 nanocomposite conduction band characteristics but different valence band features. Associated molecular orbital distributions reveal dye-to-TiO2 interfacial charge transfer in all five differing aggregate orders; meanwhile, the level of intramolecular charge transfer in the dye becomes progressively localized around its azo- and electron-donating groups, up to the tetrameric dye/TiO2 species. Dye adsorption energies and dye coverage levels are calculated and compared with experiment. Overall, the findings of this case study serve to aid the molecular design of azo dyes towards better performing DSSC devices wherein they are incorporated. In addition, they provide a helpful example reference for understanding the effects of dye aggregation on the adsorbate…TiO2 interfacial optical and electronic properties.« less

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

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.

Noncovalent binding of xanthene and phthalocyanine dyes with graphene sheets: the effect of the molecular structure revealed by a photophysical study.

PubMed

Zhang, Xian-Fu; Liu, Su-Ping; Shao, Xiao-Na

2013-09-01

The fluorescence and absorption properties of several xanthene and phthalocyanine dyes were measured in the presence and absence of chemically derived graphene (CDG) sheets. The interaction of pyronine Y (PYY) with graphene sheets was compared with that of rhodamine 6G (R6G) to reveal the effect of the molecular structure. Although the presence of the perpendicular benzene moiety in a R6G or phthalocyanine molecule does cause the difficulty for forming dye-CDG complex and make CDG less efficient in quenching the fluorescence intensity and shortening the fluorescence lifetime, it does not affect the band position of charge transfer absorption, suggesting that no molecular shape change occurred in a dye molecule caused by the interaction with CDG sheets. The spectroscopic and thermodynamic data indicated that the dye-CDG binding is of charge transfer nature, while the dynamic fluorescence quenching is due to photoinduced energy and electron transfer. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

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.

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.

Relationship between tribology and optics in thin films of mechanically oriented nanocrystals.

PubMed

Wong, Liana; Hu, Chunhua; Paradise, Ruthanne; Zhu, Zina; Shtukenberg, Alexander; Kahr, Bart

2012-07-25

Many crystalline dyes, when rubbed unidirectionally with cotton on glass slides, can be organized as thin films of highly aligned nanocrystals. Commonly, the linear birefringence and linear dichroism of these films resemble the optical properties of single crystals, indicating precisely oriented particles. Of 186 colored compounds, 122 showed sharp extinction and 50 were distinctly linearly dichroic. Of the latter 50 compounds, 88% were more optically dense when linearly polarized light was aligned with the rubbing axis. The mechanical properties of crystals that underlie the nonstatistical correlation between tribological processes and the direction of electron oscillations in absorption bands are discussed. The features that give rise to the orientation of dye crystallites naturally extend to colorless molecular crystals.

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.

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

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.

Morphological study of electrophoretically deposited TiO2 film for DSSC application

NASA Astrophysics Data System (ADS)

Patel, Alkesh B.; Patel, K. D.; Soni, S. S.; Sonigara, K. K.

2018-05-01

In the immerging field of eco-friendly and low cost photovoltaic devices, dye sensitized solar cell (DSSC) [1] has been investigated as promising alternative to the conventional silicon-based solar cells. In the DSSC device, photoanode is crucial component that take charge of holding sensitizer on it and inject the electrons from the sensitizer to current collector. Nanoporous TiO2 is the most relevant candidate for the preparation of photoanode in DSSCs. Surface properties, morphology, porosity and thickness of TiO2 film as well as preparation technique determine the performance of device. In the present work we have report the study of an effect of nanoporous anatase titanium dioxide (TiO2) film thickness on DSSC performance. Photoanode TiO2 (P25) film was deposited on conducting substrate by electrophoresis technique (EPD) and film thickness was controlled during deposition by applying different current density for a constant time interval. Thickness and surface morphology of prepared films was studied by SEM and transmittance analysis. The same set of photoanode was utilized in DSSC devices using metal free organic dye sensitizer to evaluate the photovoltaic performance. Devices were characterized through Current-Voltage (I-V) characteristic, electrochemical impedance spectroscopy (EIS) and open circuit voltage decay curves. Dependency of device performance corresponding to TiO2 film thickness is investigated through the lifetime kinetics of electron charge transfer mechanism trough impedance fitting. It is concluded that appropriate thickness along with uniformity and porosity are required to align the dye molecules to respond efficiently the incident light photons.

Efficient room-temperature source of polarized single photons

DOEpatents

Lukishova, Svetlana G.; Boyd, Robert W.; Stroud, Carlos R.

2007-08-07

An efficient technique for producing deterministically polarized single photons uses liquid-crystal hosts of either monomeric or oligomeric/polymeric form to preferentially align the single emitters for maximum excitation efficiency. Deterministic molecular alignment also provides deterministically polarized output photons; using planar-aligned cholesteric liquid crystal hosts as 1-D photonic-band-gap microcavities tunable to the emitter fluorescence band to increase source efficiency, using liquid crystal technology to prevent emitter bleaching. Emitters comprise soluble dyes, inorganic nanocrystals or trivalent rare-earth chelates.

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.

Polarization properties of below-threshold harmonics from aligned molecules H2+ in linearly polarized laser fields.

PubMed

Dong, Fulong; Tian, Yiqun; Yu, Shujuan; Wang, Shang; Yang, Shiping; Chen, Yanjun

2015-07-13

We investigate the polarization properties of below-threshold harmonics from aligned molecules in linearly polarized laser fields numerically and analytically. We focus on lower-order harmonics (LOHs). Our simulations show that the ellipticity of below-threshold LOHs depends strongly on the orientation angle and differs significantly for different harmonic orders. Our analysis reveals that this LOH ellipticity is closely associated with resonance effects and the axis symmetry of the molecule. These results shed light on the complex generation mechanism of below-threshold harmonics from aligned molecules.

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.

TMRG studies on spin alignment in molecule-based ferrimagnetics [rapid communication

NASA Astrophysics Data System (ADS)

Liu, Q. M.; Yao, K. L.; Liu, Z. L.

2005-05-01

A physical picture of spin alignment in organic molecule-based ferrimagnets is presented from studying the thermal effective magnetic moment of the sublattice by use of the transfer matrix renormalization group. We conclude that the classical antiparallel spin alignment is not the most stable state. The three-spin system tends to parallel alignment when the exchange interaction between the biradical and the monoradical molecules is much weaker than that within the biradical, which can result in the decrease of the effective magnetic moment upon lowering the temperature. More importantly, we give the theoretical evidence that even the antiparallel spin alignment in the biradical monoradical alternating chain does not necessarily lead to ferrimagnetic spin ordering due to the formation of the spin singlet pairs, which suppresses the ferrimagnetic spin alignment.

Label free biosensor incorporating a replica-molded, vertically emitting distributed feedback laser

NASA Astrophysics Data System (ADS)

Lu, M.; Choi, S. S.; Wagner, C. J.; Eden, J. G.; Cunningham, B. T.

2008-06-01

A label free biosensor based upon a vertically emitting distributed feedback (DFB) laser has been demonstrated. The DFB laser comprises a replica-molded, one-dimensional dielectric grating coated with laser dye-doped polymer as the gain medium. Adsorption of biomolecules onto the laser surface alters the DFB laser emission wavelength, thereby permitting the kinetic adsorption of a protein polymer monolayer or the specific binding of small molecules to be quantified. A bulk sensitivity of 16.6nm per refractive index unit and the detection of a monolayer of the protein polymer poly(Lys, Phe) have been observed with this biosensor. The sensor represents a departure from conventional passive resonant optical sensors from the standpoint that the device actively generates its own narrowband high intensity output without stringent requirements on the coupling alignments, resulting in a simple, robust illumination and detection configuration.

Flexible Dye-Sensitized Solar Cell Based on Vertical ZnO Nanowire Arrays

PubMed Central

2011-01-01

Flexible dye-sensitized solar cells are fabricated using vertically aligned ZnO nanowire arrays that are transferred onto ITO-coated poly(ethylene terephthalate) substrates using a simple peel-off process. The solar cells demonstrate an energy conversion efficiency of 0.44% with good bending tolerance. This technique paves a new route for building large-scale cost-effective flexible photovoltaic and optoelectronic devices. PMID:27502660

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.

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.

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.

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.

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

Measurement and statistical analysis of single-molecule current-voltage characteristics, transition voltage spectroscopy, and tunneling barrier height.

PubMed

Guo, Shaoyin; Hihath, Joshua; Díez-Pérez, Ismael; Tao, Nongjian

2011-11-30

We report on the measurement and statistical study of thousands of current-voltage characteristics and transition voltage spectra (TVS) of single-molecule junctions with different contact geometries that are rapidly acquired using a new break junction method at room temperature. This capability allows one to obtain current-voltage, conductance voltage, and transition voltage histograms, thus adding a new dimension to the previous conductance histogram analysis at a fixed low-bias voltage for single molecules. This method confirms the low-bias conductance values of alkanedithiols and biphenyldithiol reported in literature. However, at high biases the current shows large nonlinearity and asymmetry, and TVS allows for the determination of a critically important parameter, the tunneling barrier height or energy level alignment between the molecule and the electrodes of single-molecule junctions. The energy level alignment is found to depend on the molecule and also on the contact geometry, revealing the role of contact geometry in both the contact resistance and energy level alignment of a molecular junction. Detailed statistical analysis further reveals that, despite the dependence of the energy level alignment on contact geometry, the variation in single-molecule conductance is primarily due to contact resistance rather than variations in the energy level alignment.

Effect of multi-dimensional ultraviolet light exposure on the growth of pentacene film and application to organic field-effect transistors.

PubMed

Bae, Jin-Hyuk; Lee, Sin-Doo; Choi, Jong Sun; Park, Jaehoon

2012-05-01

We report on the multi-dimensional alignment of pentacene molecules on a poly(methyl methacrylate)-based photosensitive polymer (PMMA-polymer) and its effect on the electrical performance of the pentacene-based field-effect transistor (FET). Pentacene molecules are shown to be preferentially aligned on the linearly polarized ultraviolet (LPUV)-exposed PMMA-polymer layer, which is contrast to an isotropic alignment on the bare PMMA-polymer layer. Multi-dimensional alignment of pentacene molecules in the film could be achieved by adjusting the direction of LPUV exposed to the PMMA-polymer. The control of pentacene molecular alignment is found to be promising for the field-effect mobility enhancement in the pentacene FET.

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.

A molecular-field-based similarity study of non-nucleoside HIV-1 reverse transcriptase inhibitors

NASA Astrophysics Data System (ADS)

Mestres, Jordi; Rohrer, Douglas C.; Maggiora, Gerald M.

1999-01-01

This article describes a molecular-field-based similarity method for aligning molecules by matching their steric and electrostatic fields and an application of the method to the alignment of three structurally diverse non-nucleoside HIV-1 reverse transcriptase inhibitors. A brief description of the method, as implemented in the program MIMIC, is presented, including a discussion of pairwise and multi-molecule similarity-based matching. The application provides an example that illustrates how relative binding orientations of molecules can be determined in the absence of detailed structural information on their target protein. In the particular system studied here, availability of the X-ray crystal structures of the respective ligand-protein complexes provides a means for constructing an 'experimental model' of the relative binding orientations of the three inhibitors. The experimental model is derived by using MIMIC to align the steric fields of the three protein P66 subunit main chains, producing an overlay with a 1.41 Å average rms distance between the corresponding Cα's in the three chains. The inter-chain residue similarities for the backbone structures show that the main-chain conformations are conserved in the region of the inhibitor-binding site, with the major deviations located primarily in the 'finger' and RNase H regions. The resulting inhibitor structure overlay provides an experimental-based model that can be used to evaluate the quality of the direct a priori inhibitor alignment obtained using MIMIC. It is found that the 'best' pairwise alignments do not always correspond to the experimental model alignments. Therefore, simply combining the best pairwise alignments will not necessarily produce the optimal multi-molecule alignment. However, the best simultaneous three-molecule alignment was found to reproduce the experimental inhibitor alignment model. A pairwise consistency index has been derived which gauges the quality of combining the pairwise alignments and aids in efficiently forming the optimal multi-molecule alignment analysis. Two post-alignment procedures are described that provide information on feature-based and field-based pharmacophoric patterns. The former corresponds to traditional pharmacophore models and is derived from the contribution of individual atoms to the total similarity. The latter is based on molecular regions rather than atoms and is constructed by computing the percent contribution to the similarity of individual points in a regular lattice surrounding the molecules, which when contoured and colored visually depict regions of highly conserved similarity. A discussion of how the information provided by each of the procedures is useful in drug design is also presented.

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.

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.

Highly uniform and vertically aligned SnO2 nanochannel arrays for photovoltaic applications

NASA Astrophysics Data System (ADS)

Kim, Jae-Yup; Kang, Jin Soo; Shin, Junyoung; Kim, Jin; Han, Seung-Joo; Park, Jongwoo; Min, Yo-Sep; Ko, Min Jae; Sung, Yung-Eun

2015-04-01

Nanostructured electrodes with vertical alignment have been considered ideal structures for electron transport and interfacial contact with redox electrolytes in photovoltaic devices. Here, we report large-scale vertically aligned SnO2 nanochannel arrays with uniform structures, without lateral cracks fabricated by a modified anodic oxidation process. In the modified process, ultrasonication is utilized to avoid formation of partial compact layers and lateral cracks in the SnO2 nanochannel arrays. Building on this breakthrough, we first demonstrate the photovoltaic application of these vertically aligned SnO2 nanochannel arrays. These vertically aligned arrays were directly and successfully applied in quasi-solid state dye-sensitized solar cells (DSSCs) as photoanodes, yielding reasonable conversion efficiency under back-side illumination. In addition, a significantly short process time (330 s) for achieving the optimal thickness (7.0 μm) and direct utilization of the anodized electrodes enable a simple, rapid and low-cost fabrication process. Furthermore, a TiO2 shell layer was coated on the SnO2 nanochannel arrays by the atomic layer deposition (ALD) process for enhancement of dye-loading and prolonging the electron lifetime in the DSSC. Owing to the presence of the ALD TiO2 layer, the short-circuit photocurrent density (Jsc) and conversion efficiency were increased by 20% and 19%, respectively, compared to those of the DSSC without the ALD TiO2 layer. This study provides valuable insight into the development of efficient SnO2-based photoanodes for photovoltaic application by a simple and rapid fabrication process.Nanostructured electrodes with vertical alignment have been considered ideal structures for electron transport and interfacial contact with redox electrolytes in photovoltaic devices. Here, we report large-scale vertically aligned SnO2 nanochannel arrays with uniform structures, without lateral cracks fabricated by a modified anodic oxidation process. In the modified process, ultrasonication is utilized to avoid formation of partial compact layers and lateral cracks in the SnO2 nanochannel arrays. Building on this breakthrough, we first demonstrate the photovoltaic application of these vertically aligned SnO2 nanochannel arrays. These vertically aligned arrays were directly and successfully applied in quasi-solid state dye-sensitized solar cells (DSSCs) as photoanodes, yielding reasonable conversion efficiency under back-side illumination. In addition, a significantly short process time (330 s) for achieving the optimal thickness (7.0 μm) and direct utilization of the anodized electrodes enable a simple, rapid and low-cost fabrication process. Furthermore, a TiO2 shell layer was coated on the SnO2 nanochannel arrays by the atomic layer deposition (ALD) process for enhancement of dye-loading and prolonging the electron lifetime in the DSSC. Owing to the presence of the ALD TiO2 layer, the short-circuit photocurrent density (Jsc) and conversion efficiency were increased by 20% and 19%, respectively, compared to those of the DSSC without the ALD TiO2 layer. This study provides valuable insight into the development of efficient SnO2-based photoanodes for photovoltaic application by a simple and rapid fabrication process. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00202h

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.

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

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

Optical fluorescent imaging to monitor temporal effects of microbubble-mediated ultrasound therapy.

PubMed

Sorace, Anna G; Saini, Reshu; Rosenthal, Eben; Warram, Jason M; Zinn, Kurt R; Hoyt, Kenneth

2013-02-01

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.

Minimizing pulling geometry errors in atomic force microscope single molecule force spectroscopy.

PubMed

Rivera, Monica; Lee, Whasil; Ke, Changhong; Marszalek, Piotr E; Cole, Daniel G; Clark, Robert L

2008-10-01

In atomic force microscopy-based single molecule force spectroscopy (AFM-SMFS), it is assumed that the pulling angle is negligible and that the force applied to the molecule is equivalent to the force measured by the instrument. Recent studies, however, have indicated that the pulling geometry errors can drastically alter the measured force-extension relationship of molecules. Here we describe a software-based alignment method that repositions the cantilever such that it is located directly above the molecule's substrate attachment site. By aligning the applied force with the measurement axis, the molecule is no longer undergoing combined loading, and the full force can be measured by the cantilever. Simulations and experimental results verify the ability of the alignment program to minimize pulling geometry errors in AFM-SMFS studies.

Determination of dye/protein ratios in a labeling reaction between a cyanine dye and bovine serum albumin by micellar electrokinetic chromatography using a diode laser-induced fluorescence detection.

PubMed

Jing, Peng; Kaneta, Takashi; Imasaka, Totaro

2002-08-01

The degree of labeling, i.e., dye/protein ratio (D/P) is important for characterizing properties of dye labeling with proteins. A method for the determination of this ratio between a fluorescent cyanine dye and bovine serum albumin (BSA), based on the separation of the labeling mixture using micellar electrokinetic chromatography with diode laser-induced fluorescence detection, is described. Two methods for the determination of D/P were examined in this study. In these methods, a hydrolysis product and impurities, which are usually unfavorable compounds that are best excluded for protein analysis, were utilized to determine the amounts of dye bound to BSA. One is a direct method in which a ratio of the peak area of BSA to the total peak area of all the products produced in the labeling reaction was used for determining the average number of dye molecules bound to a single BSA molecule. The other is an indirect determination, which is based on diminution of all peak areas related to the products except for the labeled BSA. These methods were directly compared by means of a spectrophotometric method. The experimental results show that the indirect method is both reliable and sensitive. Therefore, D/P values can be determined at trace levels using the indirect method.

Comparative study on the process behavior and reaction kinetics in sonocatalytic degradation of organic dyes by powder and nanotubes TiO2.

PubMed

Pang, Yean Ling; Abdullah, Ahmad Zuhairi

2012-05-01

Sonocatalytic degradation of various organic dyes (Congo Red, Reactive Blue 4, Methyl Orange, Rhodamine B and Methylene Blue) catalyzed by powder and nanotubes TiO(2) was studied. Both catalysts were characterized using transmission electron microscope (TEM), surface analyzer, Raman spectroscope and thermal gravimetric analyzer (TGA). Sonocatalytic activity of powder and nanotubes TiO(2) was elucidated based on the degradation of various organic dyes. The former catalyst was favorable for treatment of anionic dyes, while the latter was more beneficial for cationic dyes. Sonocatalytic activity of TiO(2) nanotubes could be up to four times as compared to TiO(2) powder under an ultrasonic power of 100 W and a frequency of 42 kHz. This was associated with the higher surface area and the electrostatic attraction between dye molecules and TiO(2) nanotubes. Fourier transform-infrared spectrometer (FT-IR) was used to identify changes that occurred on the functional group in Rhodamine B molecules and TiO(2) nanotubes after the reaction. Sonocatalytic degradation of Rhodamine B by TiO(2) nanotubes apparently followed the Langmuir-Hinshelwood adsorption kinetic model with surface reaction rate of 1.75 mg/L min. TiO(2) nanotubes were proven for their high potential to be applied in sonocatalytic degradation of organic dyes. Copyright © 2011 Elsevier B.V. All rights reserved.

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

A combined experimental and DFT investigation of disazo dye having pyrazole skeleton

NASA Astrophysics Data System (ADS)

Şener, Nesrin; Bayrakdar, Alpaslan; Kart, Hasan Hüseyin; Şener, İzzet

2017-02-01

Disazo dye containing pyrazole skeleton has been synthesized. The structure of the dye has been confirmed by using FT-IR, 1H NMR, 13C NMR, HRMS spectral technique and elemental analysis. The molecular geometry and infrared spectrum are also calculated by the Density Functional Theory (DFT) employing B3LYP level with 6-311G (d,p) basis set. The chemical shifts calculation for 1H NMR of the title molecule is done by using by Gauge-Invariant Atomic Orbital (GIAO) method by utilizing the same basis sets. The total density of state, the partial density of state and the overlap population density of state diagram analysis are done via Gauss Sum 3.0 program. Frontier molecular orbitals such as highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) and molecular electrostatic potential surface on the title molecule are predicted for various intramolecular interactions that are responsible for the stabilization of the molecule. The experimental results and theoretical values have been compared.

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.

Strongly aligned gas-phase molecules at free-electron lasers

DOE PAGES

Kierspel, Thomas; Wiese, Joss; Mullins, Terry; ...

2015-09-16

Here, we demonstrate a novel experimental implementation to strongly align molecules at full repetition rates of free-electron lasers. We utilized the available in-house laser system at the coherent x-ray imaging beamline at the linac coherent light source. Chirped laser pulses, i.e., the direct output from the regenerative amplifier of the Ti:Sa chirped pulse amplification laser system, were used to strongly align 2, 5-diiodothiophene molecules in a molecular beam. The alignment laser pulses had pulse energies of a few mJ and a pulse duration of 94 ps. A degree of alignment ofmore » $$\\langle {\\mathrm{cos}}^{2}{\\theta }_{2{\\rm{D}}}\\rangle =0.85$$ was measured, limited by the intrinsic temperature of the molecular beam rather than by the available laser system. With the general availability of synchronized chirped-pulse-amplified near-infrared laser systems at short-wavelength laser facilities, our approach allows for the universal preparation of molecules tightly fixed in space for experiments with x-ray pulses.« less

Where to attach dye molecules to a protein: lessons from the computer program WHAT IF

NASA Astrophysics Data System (ADS)

Altenberg-Greulich, B.; Vriend, G.

2001-10-01

Genomic and proteomic projects are producing a flood of data that all require interpretation which often is best performed based on a three dimensional structure of the molecule(s) involved. These structures can be determined experimentally, or modelled by homology. Because of the complexity of the questions and the heterogeneity of the data, the software used for modelling proteins must become even more versatile. We describe several case studies in which the questions asked, the data, and the requirements on the software all are very different. It is shown how structural knowledge about a protein helps to determine the best place to bind a fluorescent dye. Such dyes are needed to determine protein-protein, protein-DNA interactions or intrinsic fluorescence microscopy. Further, using dyes you can trace molecules in the cell and thus get a handle on subcellular localisation. The first example (OCT-1) involves the search for free amino groups in a protein-DNA complex. The second example (BPTI) is a case, in which the amino acid distribution shows that amino groups are spread all over the structure, so that the natural structure has to be modified to get an answer. The third example (HFE) involves a model built by homology. In this case the amino group distribution can also be predicted. All these studies were performed using the WHAT IF software package. This package is available including source code, documentation, etc. See http://www.cmbi.kun.nl/whatif/

MALDI mass spectrometry of dye-peptide and dye-protein complexes.

PubMed

Salih, B; Zenobi, R

1998-04-15

Immobilized sulfonate dyes are widely used for protein separation and purification, but the mode of interaction between the dye molecules and the proteins is largely unknown. Here we show that specific noncovalent dye-protein and dye-peptide complexes can be observed using MALDI mass spectrometry. We prove that the interaction is prodominantly electrostatic and that it involves protonated sites of the peptides and proteins, including the NH2 terminus, and deprotonated SO3 groups of the dyes. Furthermore, we show that MALDI-MS of such complexes with a nonacidic matrix, p-nitro-aniline, can be used to determine the number of accessible basic sites of a protein or peptide in its folded structure. Our results are in good agreement with measurements of the same property done with electrospray ionization.

LS-align: an atom-level, flexible ligand structural alignment algorithm for high-throughput virtual screening.

PubMed

Hu, Jun; Liu, Zi; Yu, Dong-Jun; Zhang, Yang

2018-02-15

Sequence-order independent structural comparison, also called structural alignment, of small ligand molecules is often needed for computer-aided virtual drug screening. Although many ligand structure alignment programs are proposed, most of them build the alignments based on rigid-body shape comparison which cannot provide atom-specific alignment information nor allow structural variation; both abilities are critical to efficient high-throughput virtual screening. We propose a novel ligand comparison algorithm, LS-align, to generate fast and accurate atom-level structural alignments of ligand molecules, through an iterative heuristic search of the target function that combines inter-atom distance with mass and chemical bond comparisons. LS-align contains two modules of Rigid-LS-align and Flexi-LS-align, designed for rigid-body and flexible alignments, respectively, where a ligand-size independent, statistics-based scoring function is developed to evaluate the similarity of ligand molecules relative to random ligand pairs. Large-scale benchmark tests are performed on prioritizing chemical ligands of 102 protein targets involving 1,415,871 candidate compounds from the DUD-E (Database of Useful Decoys: Enhanced) database, where LS-align achieves an average enrichment factor (EF) of 22.0 at the 1% cutoff and the AUC score of 0.75, which are significantly higher than other state-of-the-art methods. Detailed data analyses show that the advanced performance is mainly attributed to the design of the target function that combines structural and chemical information to enhance the sensitivity of recognizing subtle difference of ligand molecules and the introduces of structural flexibility that help capture the conformational changes induced by the ligand-receptor binding interactions. These data demonstrate a new avenue to improve the virtual screening efficiency through the development of sensitive ligand structural alignments. http://zhanglab.ccmb.med.umich.edu/LS-align/. njyudj@njust.edu.cn or zhng@umich.edu. Supplementary data are available at Bioinformatics online.

On the molecular interaction between lactoferrin and the dye Red HE-3B. A novel approach for docking a charged and highly flexible molecule to protein surfaces

NASA Astrophysics Data System (ADS)

Grasselli, Mariano; Cascone, Osvaldo; Anspach, F. Birger; Delfino, Jose M.

2002-12-01

Lactoferrin (Lf) is a non-heme, iron binding protein present in many physiological fluids of vertebrates where its main role is the microbicidal activity. It has been isolated by different methods, including dye-affinity chromatography. Red HE-3B is one of the most common triazinic dyes applied in protein purification, but scant knowledge is available on structural details and on the energetics of its interaction with proteins. In this work we present a computational approach useful for identifying possible binding sites for Red HE-3B in apo and holo forms of Lfs from human and bovine source. A new geometrical description of Red HE-3B is introduced which greatly simplifies the conformational analysis. This approach proved to be of particular advantage for addressing conformational ensembles of highly flexible molecules. Predictions from this analysis were correlated with experimentally observed dye-binding sites, as mapped by protection from proteolysis in Red HE-3B/Lf complexes. This method could bear relevance for the screening of possible dye-binding sites in proteins whose structure is known and as a potential tool for the design of engineered protein variants which could be purified by dye-affinity chromatography.

On the molecular interaction between lactoferrin and the dye Red HE-3b. A novel approach for docking a charged and highly flexible molecule to protein surfaces.

PubMed

Grasselli, Mariano; Cascone, Osvaldo; Birger Anspach, F; Delfino, Jose M

2002-12-01

Lactoferrin (Lf) is a non-heme, iron binding protein present in many physiological fluids of vertebrates where its main role is the microbicidal activity. It has been isolated by different methods, including dye-affinity chromatography. Red HE-3B is one of the most common triazinic dyes applied in protein purification, but scant knowledge is available on structural details and on the energetics of its interaction with proteins. In this work we present a computational approach useful for identifying possible binding sites for Red HE-3B in apo and holo forms of Lfs from human and bovine source. A new geometrical description of Red HE-3B is introduced which greatly simplifies the conformational analysis. This approach proved to be of particular advantage for addressing conformational ensembles of highly flexible molecules. Predictions from this analysis were correlated with experimentally observed dye-binding sites, as mapped by protection from proteolysis in Red HE-3B/Lf complexes. This method could bear relevance for the screening of possible dye-binding sites in proteins whose structure is known and as a potential tool for the design of engineered protein variants which could be purified by dye-affinity chromatography.

Effects of vacuum exposure on stress and spectral shift of high reflective coatings

NASA Astrophysics Data System (ADS)

Stolz, C. J.; Taylor, J. R.; Eickelberg, W. K.; Lindh, J. D.

1992-06-01

The Atomic Vapor Laser Isotope Laser Separation (AVLIS) program operates the world's largest average power dye laser; the dye laser beams are combined, formatted, and transported in vacuum. The optical system is aligned at atmosphere, while the system must meet requirements in vacuum. Therefore, coating performance must be characterized in both atmosphere and vacuum. Changes in stress and spectral shift in ambient and vacuum environments are reported for conventional and dense multilayer dielectric coatings.

Photodegradation of malachite green dye catalyzed by Keggin-type polyoxometalates under visible-light irradiation: Transition metal substituted effects

NASA Astrophysics Data System (ADS)

Liu, Chun-Guang; Zheng, Ting; Liu, Shuang; Zhang, Han-Yu

2016-04-01

In the present paper, Keggin-type polyoxometalates (POMs) (NH4)3[PW12O40] and its mono-transition-metal-substituted species (NH4)5[{PW11O39}MII(H2O)] (M = Mn, Fe, Co, Ni, Cu, Zn) have been synthesized and used as photocatalyst to activate O2 for the degradation of dye molecule under visible-light irradiation. Because of the strong adsorption on the surface of POM catalyst, malachite green (MG) molecule was employed as a molecular probe to test their photocatalytic activity. The photodegradation study shows that introduction of transition metal ion leads to an increase in the degradation of MG in the following order: Mn < Fe < Co < [PW12O40]3- < Ni < Cu < Zn, which indicates that the photocatalytic activity of these POMs is sensitive to the transition metal substituted effects. Electronic structure analysis based on the density functional theory calculations shows that a moderate decrease of oxidizing ability of POM catalyst may improve the photocatalytic activity in the degradation of dye molecule under visible-light irradiation. Meanwhile, intermediate products about the photocatalytic oxidation of MG molecule were proposed on the basis of gas chromatograph mass spectrometer analysis.

Clinical trials in near infrared fluorescence imaging with IRDye 800CW

NASA Astrophysics Data System (ADS)

Draney, Daniel R.

2015-03-01

A monofunctional, heptamethine dye, IRDye® 800CW, is being manufactured under GMP conditions for use in human clinical trials. When attached to a suitable targeting agent and paired with an appropriate camera system, the dye allows Near Infrared (NIR) fluorescence imaging of tumor tissue during surgery. The talk will describe the properties of the dye and give an overview of current and planned clinical trials in Europe and the USA. The dye is available in both the NHS ester and carboxylate forms for conjugation to targeting molecules. A GMP toxicology study of the dye was described in a previous publication.

Aligned Immobilization of Proteins Using AC Electric Fields.

PubMed

Laux, Eva-Maria; Knigge, Xenia; Bier, Frank F; Wenger, Christian; Hölzel, Ralph

2016-03-01

Protein molecules are aligned and immobilized from solution by AC electric fields. In a single-step experiment, the enhanced green fluorescent proteins are immobilized on the surface as well as at the edges of planar nanoelectrodes. Alignment is found to follow the molecules' geometrical shape with their longitudinal axes parallel to the electric field. Simultaneous dielectrophoretic attraction and AC electroosmotic flow are identified as the dominant forces causing protein movement and alignment. Molecular orientation is determined by fluorescence microscopy based on polarized excitation of the proteins' chromophores. The chromophores' orientation with respect to the whole molecule supports X-ray crystal data. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of keratin-based microcapsules for encapsulation of hydrophilic molecules.

PubMed

Rajabinejad, Hossein; Patrucco, Alessia; Caringella, Rosalinda; Montarsolo, Alessio; Zoccola, Marina; Pozzo, Pier Davide

2018-01-01

The interest towards microcapsules based on non-toxic, biodegradable and biocompatible polymers, such as proteins, is increasing considerably. In this work, microcapsules were prepared using water soluble keratin, known as keratoses, with the aim of encapsulating hydrophilic molecules. Keratoses were obtained via oxidizing extraction of pristine wool, previously degreased by Soxhlet. In order to better understand the shell part of microcapsules, pristine wool and obtained keratoses were investigated by FT-IR, gel-electrophoresis and HPLC. Production of the microcapsules was carried out by a sonication method. Thermal properties of microcapsules were investigated by DSC. Microencapsulation and dye encapsulation yields were obtained by UV-spectroscopy. Morphological structure of microcapsules was studied by light microscopy, SEM, and AFM. The molecular weights of proteins analyzed using gel-electrophoresis resulted in the range of 38-62kDa. The results confirmed that the hydrophilic dye (Telon Blue) was introduced inside the keratoses shells by sonication and the final microcapsules diameter ranged from 0.5 to 4µm. Light microscope investigation evidenced the presence of the dye inside the keratoses vesicles, confirming their capability of encapsulating hydrophilic molecules. The microcapsule yield and dye encapsulation yield were found to be 28.87±3% and 83.62±5% respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Förster resonance energy transfer mediated enhancement of the fluorescence lifetime of organic fluorophores to the millisecond range by coupling to Mn-doped CdS/ZnS quantum dots

NASA Astrophysics Data System (ADS)

Kaiser, Uwe; Sabir, Nadeem; Carrillo-Carrion, Carolina; del Pino, Pablo; Bossi, Mariano; Heimbrodt, Wolfram; Parak, Wolfgang J.

2016-02-01

Manganese-doped CdS/ZnS quantum dots have been used as energy donors in a Förster-like resonance energy transfer (FRET) process to enhance the effective lifetime of organic fluorophores. It was possible to tune the effective lifetime of the fluorophores by about six orders of magnitude from the nanosecond (ns) up to the millisecond (ms) region. Undoped and Mn-doped CdS/ZnS quantum dots functionalized with different dye molecules were selected as a model system for investigating the multiple energy transfer process and the specific interaction between Mn ions and the attached dye molecules. While the lifetime of the free dye molecules was about 5 ns, their linking to undoped CdS/ZnS quantum dots led to a long effective lifetime of about 150 ns, following a non-exponential transient. Manganese-doped core-shell quantum dots further enhanced the long-lasting decay time of the dye to several ms. This opens up a pathway to analyse different fluorophores in the time domain with equal spectral emissions. Such lifetime multiplexing would be an interesting alternative to the commonly used spectral multiplexing in fluorescence detection schemes.

Minimizing ATP depletion by oxygen scavengers for single-molecule fluorescence imaging in live cells.

PubMed

Jung, Seung-Ryoung; Deng, Yi; Kushmerick, Christopher; Asbury, Charles L; Hille, Bertil; Koh, Duk-Su

2018-06-19

The stability of organic dyes against photobleaching is critical in single-molecule tracking and localization microscopy. Since oxygen accelerates photobleaching of most organic dyes, glucose oxidase is commonly used to slow dye photobleaching by depleting oxygen. As demonstrated here, pyranose-2-oxidase slows bleaching of Alexa647 dye by ∼20-fold. However, oxygen deprivation may pose severe problems for live cells by reducing mitochondrial oxidative phosphorylation and ATP production. We formulate a method to sustain intracellular ATP levels in the presence of oxygen scavengers. Supplementation with metabolic intermediates including glyceraldehyde, glutamine, and α-ketoisocaproate maintained the intracellular ATP level for at least 10 min by balancing between FADH 2 and NADH despite reduced oxygen levels. Furthermore, those metabolites supported ATP-dependent synthesis of phosphatidylinositol 4,5-bisphosphate and internalization of PAR2 receptors. Our method is potentially relevant to other circumstances that involve acute drops of oxygen levels, such as ischemic damage in the brain or heart or tissues for transplantation.

Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

DOE PAGES

Liu, Zhen-Fei; Egger, David A.; Refaely-Abramson, Sivan; ...

2017-02-21

The alignment of the frontier orbital energies of an adsorbed molecule with the substrate Fermi level at metal-organic interfaces is a fundamental observable of significant practical importance in nanoscience and beyond. Typical density functional theory calculations, especially those using local and semi-local functionals, often underestimate level alignment leading to inaccurate electronic structure and charge transport properties. Here, we develop a new fully self-consistent predictive scheme to accurately compute level alignment at certain classes of complex heterogeneous molecule-metal interfaces based on optimally tuned range-separated hybrid functionals. Starting from a highly accurate description of the gas-phase electronic structure, our method by constructionmore » captures important nonlocal surface polarization effects via tuning of the long-range screened exchange in a range-separated hybrid in a non-empirical and system-specific manner. We implement this functional in a plane-wave code and apply it to several physisorbed and chemisorbed molecule-metal interface systems. Our results are in quantitative agreement with experiments, the both the level alignment and work function changes. This approach constitutes a new practical scheme for accurate and efficient calculations of the electronic structure of molecule-metal interfaces.« less

Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

NASA Astrophysics Data System (ADS)

Liu, Zhen-Fei; Egger, David A.; Refaely-Abramson, Sivan; Kronik, Leeor; Neaton, Jeffrey B.

2017-03-01

The alignment of the frontier orbital energies of an adsorbed molecule with the substrate Fermi level at metal-organic interfaces is a fundamental observable of significant practical importance in nanoscience and beyond. Typical density functional theory calculations, especially those using local and semi-local functionals, often underestimate level alignment leading to inaccurate electronic structure and charge transport properties. In this work, we develop a new fully self-consistent predictive scheme to accurately compute level alignment at certain classes of complex heterogeneous molecule-metal interfaces based on optimally tuned range-separated hybrid functionals. Starting from a highly accurate description of the gas-phase electronic structure, our method by construction captures important nonlocal surface polarization effects via tuning of the long-range screened exchange in a range-separated hybrid in a non-empirical and system-specific manner. We implement this functional in a plane-wave code and apply it to several physisorbed and chemisorbed molecule-metal interface systems. Our results are in quantitative agreement with experiments, the both the level alignment and work function changes. Our approach constitutes a new practical scheme for accurate and efficient calculations of the electronic structure of molecule-metal interfaces.

Enhancement of Fluorescence and Raman Scattering in Cyanine-Dye Molecules on the Surface of Silicon-Coated Silver Nanoparticles

NASA Astrophysics Data System (ADS)

Kamalieva, A. N.; Toropov, N. A.; Bogdanov, K. V.; Vartanyan, T. A.

2018-03-01

A method of formation of a composite structure based on silver nanoparticles and a thin protective silicon film (Ag NPs/Si) is developed. Enhancement of the fluorescence and Raman scattering in cyaninedye molecules deposited onto the formed nanostructure is observed. The optical properties and morphology stability of particles that are in contact with cyanine-dye solutions in organic solvents are studied. It is shown that the Ag NPs/Si composite structure can be multiply used as an SERS-active surface.

Automated insertion of sequences into a ribosomal RNA alignment: An application of computational linguistics in molecular biology

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

Taylor, R.C.

This thesis involved the construction of (1) a grammar that incorporates knowledge on base invariancy and secondary structure in a molecule and (2) a parser engine that uses the grammar to position bases into the structural subunits of the molecule. These concepts were combined with a novel pinning technique to form a tool that semi-automates insertion of a new species into the alignment for the 16S rRNA molecule (a component of the ribosome) maintained by Dr. Carl Woese's group at the University of Illinois at Urbana. The tool was tested on species extracted from the alignment and on a groupmore » of entirely new species. The results were very encouraging, and the tool should be substantial aid to the curators of the 16S alignment. The construction of the grammar was itself automated, allowing application of the tool to alignments for other molecules. The logic programming language Prolog was used to construct all programs involved. The computational linguistics approach used here was found to be a useful way to attach the problem of insertion into an alignment.« less

Automated insertion of sequences into a ribosomal RNA alignment: An application of computational linguistics in molecular biology

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

Taylor, Ronald C.

This thesis involved the construction of (1) a grammar that incorporates knowledge on base invariancy and secondary structure in a molecule and (2) a parser engine that uses the grammar to position bases into the structural subunits of the molecule. These concepts were combined with a novel pinning technique to form a tool that semi-automates insertion of a new species into the alignment for the 16S rRNA molecule (a component of the ribosome) maintained by Dr. Carl Woese`s group at the University of Illinois at Urbana. The tool was tested on species extracted from the alignment and on a groupmore » of entirely new species. The results were very encouraging, and the tool should be substantial aid to the curators of the 16S alignment. The construction of the grammar was itself automated, allowing application of the tool to alignments for other molecules. The logic programming language Prolog was used to construct all programs involved. The computational linguistics approach used here was found to be a useful way to attach the problem of insertion into an alignment.« 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.

Optical properties of anthocyanin dyes on TiO2 as photosensitizers for application of dye-sensitized solar cell (DSSC)

NASA Astrophysics Data System (ADS)

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

2018-03-01

Dye-sensitized solar cell (DSSC) is one of the alternative energy that can convert light energy into electrical energy. The component of DSSC consists of FTO substrates, TiO2, electrolyte, dye sensitizer, and counter electrode. This study aim was to determine the effect of optical properties of anthocyanin dyes on efficiency of DSSC. The dye sensitizer used can be extracted from anthocyanin pigments such as dragon fruit, black rice, and red cabbage. The red cabbage sensitizer shows lower absorbance value in the visible range (450-580 nm), than dragon fruit and black rice. The chemical structure of each dye molecules has an R group (carbonyl and hydroxyl) that forms a bond with the oxide layer. Red cabbage dye cell has the highest efficiency, 0.06% then dragon fruit and black rice, 0.02% and 0.03%.

The optical biomedical sensors for DNA detection and imaging based on two-photon excited luminescent styryl dyes: phototoxic influence on the DNA

NASA Astrophysics Data System (ADS)

Yashchuk, Valeriy M.; Kudrya, Vladislav Yu.; Losytskyy, Mykhaylo Yu.; Tokar, Valentyna P.; Yarmoluk, Sergiy M.; Dmytruk, Igor M.; Prokopets, Vadym M.; Kovalska, Vladyslava B.; Balanda, Anatoliy O.; Kryvorotenko, Dmytro V.; Ogul'chansky, Tymish Yu.

2007-06-01

The optical absorption, fluorescence and phosphorescence of the novel styryl dyes developed for the fluorescent detection of DNA were investigated. The energy structures of dye molecules as well as spectral manifestations of the dyes aggregate formation and interaction with DNA were studied. The dramatic increase (up to 1000 times) of the fluorescence intensity of dyes in the presence of DNA was observed. The photostability and phototoxic influence on the DNA of several styryl dyes were studied by analyzing absorption, fluorescence and phosphorescence spectra of these dyes and dye-DNA systems. Changes of the optical density value of dye-DNA solutions caused by the visible light irradiation were fixed in the wavelength regions of the DNA absorption and of the dye absorption. Fluorescence emission of dye-DNA complexes upon two-photon excitation (TPE) at wavelength 1064 nm with the 20 ns pulsed YAG: Nd3+ laser and at 840 nm with the 90 fs pulsed Ti:sapphire laser was registered. The values of two-photon absorption cross-sections of dye-DNA complexes were evaluated.

Basic quantitative polymerase chain reaction using real-time fluorescence measurements.

PubMed

Ares, Manuel

2014-10-01

This protocol uses quantitative polymerase chain reaction (qPCR) to measure the number of DNA molecules containing a specific contiguous sequence in a sample of interest (e.g., genomic DNA or cDNA generated by reverse transcription). The sample is subjected to fluorescence-based PCR amplification and, theoretically, during each cycle, two new duplex DNA molecules are produced for each duplex DNA molecule present in the sample. The progress of the reaction during PCR is evaluated by measuring the fluorescence of dsDNA-dye complexes in real time. In the early cycles, DNA duplication is not detected because inadequate amounts of DNA are made. At a certain threshold cycle, DNA-dye complexes double each cycle for 8-10 cycles, until the DNA concentration becomes so high and the primer concentration so low that the reassociation of the product strands blocks efficient synthesis of new DNA and the reaction plateaus. There are two types of measurements: (1) the relative change of the target sequence compared to a reference sequence and (2) the determination of molecule number in the starting sample. The first requires a reference sequence, and the second requires a sample of the target sequence with known numbers of the molecules of sequence to generate a standard curve. By identifying the threshold cycle at which a sample first begins to accumulate DNA-dye complexes exponentially, an estimation of the numbers of starting molecules in the sample can be extrapolated. © 2014 Cold Spring Harbor Laboratory Press.

Intrinsically Labeled Fluorescent Oligonucleotide Probes on Quantum Dots for Transduction of Nucleic Acid Hybridization.

PubMed

Shahmuradyan, Anna; Krull, Ulrich J

2016-03-15

Quantum dots (QDs) have been widely used in chemical and biosensing due to their unique photoelectrical properties and are well suited as donors in fluorescence resonance energy transfer (FRET). Selective hybridization interactions of oligonucleotides on QDs have been determined by FRET. Typically, the QD-FRET constructs have made use of labeled targets or have implemented labeled sandwich format assays to introduce dyes in proximity to the QDs for the FRET process. The intention of this new work is to explore a method to incorporate the acceptor dye into the probe molecule. Thiazole orange (TO) derivatives are fluorescent intercalating dyes that have been used for detection of double-stranded nucleic acids. One such dye system has been reported in which single-stranded oligonucleotide probes were doubly labeled with adjacent thiazole orange derivatives. In the absence of the fully complementary (FC) oligonucleotide target, the dyes form an H-aggregate, which results in quenching of fluorescence emission due to excitonic interactions between the dyes. The hybridization of the FC target to the probe provides for dissociation of the aggregate as the dyes intercalate into the double stranded duplex, resulting in increased fluorescence. This work reports investigation of the dependence of the ratiometric signal on the type of linkage used to conjugate the dyes to the probe, the location of the dye along the length of the probe, and the distance between adjacent dye molecules. The limit of detection for 34mer and 90mer targets was found to be identical and was 10 nM (2 pmol), similar to analogous QD-FRET using labeled oligonucleotide target. The detection system could discriminate a one base pair mismatch (1BPM) target and was functional without substantial compromise of the signal in 75% serum. The 1BPM was found to reduce background signal, indicating that the structure of the mismatch affected the environment of the intercalating dyes.

Bacterial decolorization of textile dyes is an extracellular process requiring a multicomponent electron transfer pathway

PubMed Central

Brigé, Ann; Motte, Bart; Borloo, Jimmy; Buysschaert, Géraldine; Devreese, Bart; Van Beeumen, Jozef J.

2008-01-01

Summary Many studies have reported microorganisms as efficient biocatalysts for colour removal of dye‐containing industrial wastewaters. We present the first comprehensive study to identify all molecular components involved in decolorization by bacterial cells. Mutants from the model organism Shewanella oneidensis MR‐1, generated by random transposon and targeted insertional mutagenesis, were screened for defects in decolorization of an oxazine and diazo dye. We demonstrate that decolorization is an extracellular reduction process requiring a multicomponent electron transfer pathway that consists of cytoplasmic membrane, periplasmic and outer membrane components. The presence of melanin, a redox‐active molecule excreted by S. oneidensis, was shown to enhance the dye reduction rates. Menaquinones and the cytochrome CymA are the crucial cytoplasmic membrane components of the pathway, which then branches off via a network of periplasmic cytochromes to three outer membrane cytochromes. The key proteins of this network are MtrA and OmcB in the periplasm and outer membrane respectively. A model of the complete dye reduction pathway is proposed in which the dye molecules are reduced by the outer membrane cytochromes either directly or indirectly via melanin. PMID:21261820

Coulombic interactions on the deposition and rotational mobility distributions of dyes in polyelectrolyte multilayer thin films.

PubMed

Li, Ye; Yip, Wai Tak

2004-12-07

We employed negatively charged fluorescein (FL), positively charged rhodamine 6G (R6G), and neutral Nile Red (NR) as molecular probes to investigate the influence of Coulombic interaction on their deposition into and rotational mobility inside polyelectrolyte multilayer (PEM) films. The entrapment efficiency of the dyes reveals that while Coulombic repulsion has little effect on dye deposition, Coulombic attraction can dramatically enhance the loading efficiency of dyes into a PEM film. By monitoring the emission polarization of single dye molecules in polyethylenimine (PEI) films, the percentages of mobile R6G, NR, and FL were determined to be 87 +/- 4%, 76 +/- 5%, and 68 +/- 3%, respectively. These mobility distributions suggest that cationic R6G enjoys the highest degree of rotational freedom, whereas anionic FL shows the least mobility because of Coulombic attraction toward cationic PEI. Regardless of charges, this high percentage of mobile molecules is in stark contrast to the 5-40% probe mobility reported from spun-cast polymer films, indicating that our PEI films contain more free volume and display richer polymer dynamics. These observations demonstrate the potential of using isolated fluorescent probes to interrogate the internal structure of a PEM film at a microscopic level.

Stabilization of He2(A(sup 3)Sigma(sub u)(+)) molecules in liquid helium by optical pumping for vacuum UV laser

NASA Technical Reports Server (NTRS)

Zmuidzinas, J. S. (Inventor)

1978-01-01

A technique is disclosed for achieving large populations of metastable spin-aligned He2(a 3 Sigma u +) molecules in superfluid helium to obtain lasing in the vacuum ultraviolet wavelength regime around 0.0800 micron m by electronically exciting liquid (superfluid) helium with a comparatively low-current electron beam and spin aligning the metastable molecules by means of optical pumping with a modestly-powered (100mW) circularly-polarized continuous wave laser operating at, for example, 0.9096 or 0.4650 micron m. Once a high concentration of spin-aligned He2 (a 3 Sigma u +) is achieved with lifetimes of a few milliseconds, a strong microwave signal destroys the spin alignment and induces a quick collisional transition of He2 (a 3 Sigma u +) molecules to the a 1 Sigma u + state and thereby a lasing transition to the X 1 Sigma g + state.

Three-dimensional single-molecule localization with nanometer accuracy using Metal-Induced Energy Transfer (MIET) imaging

NASA Astrophysics Data System (ADS)

Karedla, Narain; Chizhik, Anna M.; Stein, Simon C.; Ruhlandt, Daja; Gregor, Ingo; Chizhik, Alexey I.; Enderlein, Jörg

2018-05-01

Our paper presents the first theoretical and experimental study using single-molecule Metal-Induced Energy Transfer (smMIET) for localizing single fluorescent molecules in three dimensions. Metal-Induced Energy Transfer describes the resonant energy transfer from the excited state of a fluorescent emitter to surface plasmons in a metal nanostructure. This energy transfer is strongly distance-dependent and can be used to localize an emitter along one dimension. We have used Metal-Induced Energy Transfer in the past for localizing fluorescent emitters with nanometer accuracy along the optical axis of a microscope. The combination of smMIET with single-molecule localization based super-resolution microscopy that provides nanometer lateral localization accuracy offers the prospect of achieving isotropic nanometer localization accuracy in all three spatial dimensions. We give a thorough theoretical explanation and analysis of smMIET, describe its experimental requirements, also in its combination with lateral single-molecule localization techniques, and present first proof-of-principle experiments using dye molecules immobilized on top of a silica spacer, and of dye molecules embedded in thin polymer films.

Manipulating energy transfer in copolymer-based nanocomposites by their controlled nanocaging and release of an ionic styryl dye: a case of an ultrasensitive pH sensor.

PubMed

Manna, Anamika; Sahoo, Dibakar; Chakravorti, Sankar

2012-03-01

We report an interesting pH-tunable energy transfer between an acceptor ionic styryl dye 2-(4-(dimethylamino)styryl)-1-methylpyridinium iodide and a donor charge-transfer dye 1,8-naphthalimide in a vesicular medium. The polyethylene-b-polyethylene glycol block copolymer intercalates with the sodium dodecyl sulfate anionic surfactant to form self-aggregated nanocomposites. These nanocomposites interact with the donor molecules in aqueous solution to form "vesicles", and the donor molecules become attached on the outer wall by hydrogen bonding. The acceptor molecules are observed to be loaded in the vesicular interior. By controlling the spectral overlap of the donor and acceptor molecules by changing the pH of the medium, the energy-transfer efficiency in vesicles has been studied. The efficiency of energy transfer in vesicular media (55%) is found to be less compared to that in aqueous media (80%) at pH 7. The fall in efficiency has been attributed to the perturbation imparted by the vesicular wall due to the good matching of the donor-acceptor distance with the wall thickness. At low pH, the efficiency shows an abrupt increase (95%) due to the release of the acceptor molecules from the vesicular medium causing subsequent reduction of donor-acceptor separation and an increase of the spectral overlap at that pH.

Mixed titanium, silicon, and aluminum oxide nanostructures as novel adsorbent for removal of rhodamine 6G and methylene blue as cationic dyes from aqueous solution.

PubMed

Pal, Umapada; Sandoval, Alberto; Madrid, Sergio Isaac Uribe; Corro, Grisel; Sharma, Vivek; Mohanty, Paritosh

2016-11-01

Mixed oxide nanoparticles containing Ti, Si, and Al of 8-15 nm size range were synthesized using a combined sol-gel - hydrothermal method. Effects of composition on the structure, morphology, and optical properties of the nanoparticles were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), microRaman spectroscopy, and diffuse reflectance spectroscopy (DRS). Dye removal abilities of the nanoparticles from aqueous solutions were tested for different cationic dyes. While all the mixed oxide nanoparticles revealed high and fast adsorption of cationic dyes, the particles containing Ti and Si turned out to be the best. The adsorption kinetics and equilibrium adsorption behavior of the adsorbate - adsorbent systems could be well described by pseudo-second-order kinetics and Langmuir isotherm model, respectively. Estimated thermodynamic parameters revealed the adsorption process is spontaneous, driven mainly by the electrostatic force between the cationic dye molecules and negative charge at nanoparticle surface. Highest dye adsorption capacity (162.96 mg MB/g) of the mixed oxide nanostructures containing Ti and Si is associated to their high specific surface area, and the presence of surface Si-O(δ-) groups, in addition to the hydroxyl groups of amorphous titania. Mixed oxide nanoparticles containing 75% Ti and 25% Si seen to be the most efficient adsorbents for removing cationic dye molecules from wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Accessing the molecular frame through strong-field alignment of distributions of gas phase molecules

NASA Astrophysics Data System (ADS)

Reid, Katharine L.

2018-03-01

A rationale for creating highly aligned distributions of molecules is that it enables vector properties referenced to molecule-fixed axes (the molecular frame) to be determined. In the present work, the degree of alignment that is necessary for this to be achieved in practice is explored. Alignment is commonly parametrized in experiments by a single parameter, ?, which is insufficient to enable predictive calculations to be performed. Here, it is shown that, if the full distribution of molecular axes takes a Gaussian form, this single parameter can be used to determine the complete set of alignment moments needed to characterize the distribution. In order to demonstrate the degree of alignment that is required to approach the molecular frame, the alignment moments corresponding to a few chosen values of ? are used to project a model molecular frame photoelectron angular distribution into the laboratory frame. These calculations show that ? needs to approach 0.9 in order to avoid significant blurring to be caused by averaging. This article is part of the theme issue `Modern theoretical chemistry'.

Optical determination of charge transfer times from indoline dyes to ZnO in solid state dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Meyenburg, I.; Hofeditz, N.; Ruess, R.; Rudolph, M.; Schlettwein, D.; Heimbrodt, W.

2018-05-01

We studied the electron transfer at the interface of organic-inorganic hybrids consisting of indoline derivatives (D149 and D131) on ZnO substrates using a new optical method. We revealed the electron transfer times from the excited dye, e.g. the excitons formed in the dye aggregates to the ZnO substrate by analyzing the photoluminescence transients of the excitons after femtosecond excitation and applying kinetic model calculations. We reveal the changes of the electron transfer times by applying electrical bias. Pushing the Fermi energy of the ZnO substrate towards the excited dye level the transfer time gets longer and eventually the electron transfer is suppressed. The level alignment between the excited dye state and the ZnO Fermi-level is estimated. The excited state of D131 is about 100 meV higher than the respective state of D149 compared to the ZnO conduction band. This leads to shorter electron transfer times and eventually to higher quantum efficiencies of the solar cells.

A Rationally Designed, General Strategy for Membrane Orientation of Photoinduced Electron Transfer-Based Voltage-Sensitive Dyes.

PubMed

Kulkarni, Rishikesh U; Yin, Hang; Pourmandi, Narges; James, Feroz; Adil, Maroof M; Schaffer, David V; Wang, Yi; Miller, Evan W

2017-02-17

Voltage imaging with fluorescent dyes offers promise for interrogating the complex roles of membrane potential in coordinating the activity of neurons in the brain. Yet, low sensitivity often limits the broad applicability of optical voltage indicators. In this paper, we use molecular dynamics (MD) simulations to guide the design of new, ultrasensitive fluorescent voltage indicators that use photoinduced electron transfer (PeT) as a voltage-sensing switch. MD simulations predict an approximately 16% increase in voltage sensitivity resulting purely from improved alignment of dye with the membrane. We confirm this theoretical finding by synthesizing 9 new voltage-sensitive (VoltageFluor, or VF) dyes and establishing that all of them display the expected improvement of approximately 19%. This synergistic outworking of theory and experiment enabled computational and theoretical estimation of VF dye orientation in lipid bilayers and has yielded the most sensitive PeT-based VF dye to date. We use this new voltage indicator to monitor voltage spikes in neurons from rat hippocampus and human pluripotent-stem-cell-derived dopaminergic neurons.

Expression, purification and crystallization of a dye-decolourizing peroxidase from Dictyostelium discoideum.

PubMed

Rai, Amrita; Fedorov, Roman; Manstein, Dietmar J

2014-02-01

Dye-decolourizing peroxidases are haem-containing peroxidases with broad substrate specificity. Using H2O2 as an electron acceptor, they efficiently decolourize various dyes that are of industrial and environmental relevance, such as anthraquninone- and azo-based dyes. In this study, the dye-decolourizing peroxidase DdDyP from Dictyostelium discoideum was overexpressed in Escherichia coli strain Rosetta(DE3)pLysS, purified and crystallized using the vapour-diffusion method. A native crystal diffracted to 1.65 Å resolution and belonged to space group P4(1)2(1)2, with unit-cell parameters a = b = 141.03, c = 95.56 Å, α = β = γ = 90°. The asymmetric unit contains two molecules.

On the nature of the lowest electron transitions in the borine dye derivatives benz[cd]indole

NASA Astrophysics Data System (ADS)

Kachkovsky, O. D.; Yashchuk, V. M.; Navozenko, O. M.; Naumenko, A. P.; Slominskii, Yu. L.

2014-09-01

The fluorescence and absorption spectra of new boron-containing dyes have been analyzed in detail basing on the results of quantum chemical calculations that were performed to obtain the equilibrium molecular geometry and electron structure of the dye molecules. It has been found that the cyclization of both terminal groups by BF2 bridge changes the total charge in the symmetrical dyes and practically does not change the bond lengths in the π-electron system which increases the quantum yield of fluorescence. The possibility to vary the absorption region and total neutral charge makes these dyes promising for using as additives in light emitting layers of OLED deposited by vacuum evaporation.

LASERS, ACTIVE MEDIA: The aqueous-polyelectrolyte dye solution as an active laser medium

NASA Astrophysics Data System (ADS)

Akimov, A. I.; Saletskii, A. M.

2000-11-01

The spectral, luminescent, and lasing properties of aqueous solutions of a cationic dye rhodamine 6G with additions of anion polyelectrolytes — polyacrylic and polymethacrylic acids — are studied. It is found that the energy and spectral properties of lasing of these solutions depend on the ratio of concentrations of polyelectrolyte and molecules. It is also found that the lasing parameters of aqueous-polyelectrolyte dye solutions can be controlled by changing the structure of the molecular system. The variation in the structure of aqueous-polyelectrolyte dye solutions of rhodamine 6G resulted in an almost five-fold increase in the lasing efficiency compared to that in aqueous dye solutions.

A post-labeling strategy based on dye-induced peeling of the aptamer off single-walled carbon nanotubes for electrochemical aptasensing.

PubMed

Fu, Yingchun; Wang, Ting; Bu, Lijuan; Xie, Qingji; Li, Penghao; Chen, Jinhua; Yao, Shouzhuo

2011-03-07

A simple and efficient post-labeling strategy based on dye-induced peeling of the aptamer molecules off single-walled carbon nanotubes was developed for electrochemical aptasensing of thrombin with a detection limit down to 3 pM.

Dye-sensitized solar cells using natural dyes as sensitizers from Malaysia local fruit `Buah Mertajam'

NASA Astrophysics Data System (ADS)

Hambali, N. A. M. Ahmad; Roshidah, N.; Hashim, M. Norhafiz; Mohamad, I. S.; Saad, N. Hidayah; Norizan, M. N.

2015-05-01

We experimentally demonstrate the high conversion efficiency, low cost, green technology and easy to fabricate dye-sensitized solar cells (DSSCs) using natural anthocyanin dyes as sensitizers. The DSSCs was fabricated by using natural anthocyanin dyes which were extracted from different parts of the plants inclusive `Buah Mertajam', `Buah Keriang Dot', `Bunga Geti', Hibiscus, Red Spinach and Henna. The natural anthocyanin dyes that found in flower, leaves and fruits were extracted by the simple procedures. This anthocyanin dye is used to replace the expensive chemical synthetic dyes due to its ability to effectively attach into the surface of Titanium dioxide (TiO2). A natural anthocyanin dyes molecule adsorbs to each particle of the TiO2 and acts as the absorber of the visible light. A natural anthocyanin dye from Buah Mertajam shows the best performance with the conversion efficiency of 5.948% and fill factor of 0.708 followed by natural anthocyanin dyes from `Buah Keriang Dot', `Bunga Geti', Hibiscus, Red Spinach and Henna. Buah Mertajam or scientifically known as eriglossum rubiginosum is a local Malaysia fruit.

Dendrimer probes for enhanced photostability and localization in fluorescence imaging.

PubMed

Kim, Younghoon; Kim, Sung Hoon; Tanyeri, Melikhan; Katzenellenbogen, John A; Schroeder, Charles M

2013-04-02

Recent advances in fluorescence microscopy have enabled high-resolution imaging and tracking of single proteins and biomolecules in cells. To achieve high spatial resolutions in the nanometer range, bright and photostable fluorescent probes are critically required. From this view, there is a strong need for development of advanced fluorescent probes with molecular-scale dimensions for fluorescence imaging. Polymer-based dendrimer nanoconjugates hold strong potential to serve as versatile fluorescent probes due to an intrinsic capacity for tailored spectral properties such as brightness and emission wavelength. In this work, we report a new, to our knowledge, class of molecular probes based on dye-conjugated dendrimers for fluorescence imaging and single-molecule fluorescence microscopy. We engineered fluorescent dendritic nanoprobes (FDNs) to contain multiple organic dyes and reactive groups for target-specific biomolecule labeling. The photophysical properties of dye-conjugated FDNs (Cy5-FDNs and Cy3-FDNs) were characterized using single-molecule fluorescence microscopy, which revealed greatly enhanced photostability, increased probe brightness, and improved localization precision in high-resolution fluorescence imaging compared to single organic dyes. As proof-of-principle demonstration, Cy5-FDNs were used to assay single-molecule nucleic acid hybridization and for immunofluorescence imaging of microtubules in cytoskeletal networks. In addition, Cy5-FDNs were used as reporter probes in a single-molecule protein pull-down assay to characterize antibody binding and target protein capture. In all cases, the photophysical properties of FDNs resulted in enhanced fluorescence imaging via improved brightness and/or photostability. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Effect of dye localization and self-interactions on the photosensitized generation of singlet oxygen by rose bengal bound to bovine serum albumin.

PubMed

Turbay, María Beatriz Espeche; Rey, Valentina; Argañaraz, Natalia M; Morán Vieyra, Faustino E; Aspée, Alexis; Lissi, Eduardo A; Borsarelli, Claudio D

2014-12-01

The spectroscopic and photophysical properties of rose bengal (RB) encased in bovine serum albumin (BSA) have been examined to evaluate the photosensitized generation of singlet molecular oxygen ((1)O2). The results show that RB photophysical and photosensitizing properties are highly modulated by the average number of dye molecules per protein (n). At n ≪ 1, the dye molecule is tightly located into the hydrophobic nanocavity site I of the BSA molecule with a binding constant Kb = 0.15 ± 0.01 μM(-1). The interaction with surrounding amino acids induces heterogeneous decay of both singlet and triplet excited states of RB and partially reduce its triplet quantum yield as compared with that in buffer solution. However, despite of the diffusive barrier imposed by the protein nanocavity to (3)O2, the quenching of (3)RB(∗):BSA generates (1)O2 with quantum yield ΦΔ = 0.35 ± 0.05. In turns, the intraprotein generated (1)O2 is able to diffuse through the bulk solution, where is dynamically quenched by BSA itself with an overall quenching rate constant of 7.3 × 10(8) M(-1) s(-1). However, at n>1, nonspecific binding of up to ≈ 6RB molecules per BSA is produced, allowing efficient static quenching of excited states of RB preventing photosensitization of (1)O2. These results provide useful information for development of dye-protein adducts suitable for using as potential intracellular photosensitizers. Copyright © 2014 Elsevier B.V. All rights reserved.

A general method for controlling and resolving rotational orientation of molecules in molecule-surface collisions

PubMed Central

Godsi, Oded; Corem, Gefen; Alkoby, Yosef; Cantin, Joshua T.; Krems, Roman V.; Somers, Mark F.; Meyer, Jörg; Kroes, Geert-Jan; Maniv, Tsofar; Alexandrowicz, Gil

2017-01-01

The outcome of molecule–surface collisions can be modified by pre-aligning the molecule; however, experiments accomplishing this are rare because of the difficulty of preparing molecules in aligned quantum states. Here we present a general solution to this problem based on magnetic manipulation of the rotational magnetic moment of the incident molecule. We apply the technique to the scattering of H2 from flat and stepped copper surfaces. We demonstrate control of the molecule's initial quantum state, allowing a direct comparison of differences in the stereodynamic scattering from the two surfaces. Our results show that a stepped surface exhibits a much larger dependence of the corrugation of the interaction on the alignment of the molecule than the low-index surface. We also demonstrate an extension of the technique that transforms the set-up into an interferometer, which is sensitive to molecular quantum states both before and after the scattering event. PMID:28480890

Theoretical studies on a new pattern of laser-driven systems: towards elucidation of direct photo-injection in dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Mishima, Kenji; Yamashita, Koichi

2011-03-01

We theoretically and numerically investigated a new type of analytically solvable laser-driven systems inspired by electron-injection dynamics in dye-sensitized solar cells. The simple analytical expressions were found to be useful for understanding the difference between dye excitation and direct photo-injection occurring between dye molecule and semiconductor nanoparticles. More importantly, we propose a method for discriminating experimentally dye excitation and direct photo-injection by using time-dependent fluorescence. We found that dye excitation shows no significant quantum beat whereas the direct photo-injection shows a significant quantum beat. This work was supported by Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST) ``Development of Organic Photovoltaics toward a Low-Carbon Society,'' Cabinet Office, Japan.

Multicolor, Fluorescent Supercapacitor Fiber.

PubMed

Liao, Meng; Sun, Hao; Zhang, Jing; Wu, Jingxia; Xie, Songlin; Fu, Xuemei; Sun, Xuemei; Wang, Bingjie; Peng, Huisheng

2017-10-05

Fiber-shaped supercapacitors have attracted broad attentions from both academic and industrial communities due to the demonstrated potentials as next-generation power modules. However, it is important while remains challenging to develop dark-environment identifiable supercapacitor fibers for enhancement on operation convenience and security in nighttime applications. Herein, a novel family of colorful fluorescent supercapacitor fibers has been produced from aligned multi-walled carbon nanotube sheets. Fluorescent dye particles are introduced and stably anchored on the surfaces of aligned multi-walled carbon nanotubes to prepare hybrid fiber electrodes with a broad range of colors from red to purple. The fluorescent component in the dye introduces fluorescent indication capability to the fiber, which is particularly promising for flexible and wearable devices applied in dark environment. In addition, the colorful fluorescent supercapacitor fibers also maintain high electrochemical performance under cyclic bending and charge-discharge processes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Voltage-sensitive styryl dyes as singlet oxygen targets on the surface of bilayer lipid membrane.

PubMed

Sokolov, V S; Gavrilchik, A N; Kulagina, A O; Meshkov, I N; Pohl, P; Gorbunova, Yu G

2016-08-01

Photosensitizers are widely used as photodynamic therapeutic agents killing cancer cells by photooxidation of their components. Development of new effective photosensitive molecules requires profound knowledge of possible targets for reactive oxygen species, especially for its singlet form. Here we studied photooxidation of voltage-sensitive styryl dyes (di-4-ANEPPS, di-8-ANEPPS, RH-421 and RH-237) by singlet oxygen on the surface of bilayer lipid membranes commonly used as cell membrane models. Oxidation was induced by irradiation of a photosensitizer (aluminum phthalocyanine tetrasulfonate) and monitored by the change of dipole potential on the surface of the membrane. We studied the drop of the dipole potential both in the case when the dye molecules were adsorbed on the same side of the lipid bilayer as the photosensitizer (cis-configuration) and in the case when they were adsorbed on the opposite side (trans-configuration). Based on a simple model, we determined the rate of oxidation of the dyes from the kinetics of change of the potential during and after irradiation. This rate is proportional to steady-state concentration of singlet oxygen in the membrane under irradiation. Comparison of the oxidation rates of various dyes reveals that compounds of ANEPPS series are more sensitive to singlet oxygen than RH type dyes, indicating that naphthalene group is primarily responsible for their oxidation. Copyright © 2016 Elsevier B.V. All rights reserved.

Photocatalytic degradation of Orange G dye under solar light using nanocrystalline semiconductor metal oxide.

PubMed

Thennarasu, G; Kavithaa, S; Sivasamy, A

2011-08-01

The photocatalytic degradation of Orange G (OG) dye has been investigated using synthesised nanocrystalline ZnO as a photocatalyst and sunlight as the irradiation source. The formation of ZnO prepared from its precursor was confirmed through FT-IR and powder X-ray diffraction analyses. Surface morphology was characterised by scanning electron microscope and transmission electron microscope analysis. Band gap energy of synthesised nanocrystalline ZnO was calculated using diffuse reflectance spectroscopy (DRS). Different experimental parameters such as effects of pH, dye concentrations and mass of catalyst were standardised in order to achieve complete degradation of the dye molecules under solar light irradiation. The kinetics of oxidation of OG was also studied. The complete degradation of OG was evident after 90 min of irradiation at an initial pH of 6.86. The degradation of OG was confirmed by UV-Visible spectrophotometer, high-pressure liquid chromatography, ESI-Mass and chemical oxygen demand analyses. The adsorption of dye onto catalytic surface was analysed employing model equations such as Langmuir and Freundlich isotherms, and it was found that the Langmuir isotherm model best fitted the adsorption data. The solar photodegradation of OG followed pseudo-first-order kinetics. HPLC and ESI-Mass analyses of the degraded samples suggested that the dye molecules were readily degraded under solar irradiation with nanocrystalline ZnO.

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.

The energy level alignment at metal–molecule interfaces using Wannier–Koopmans method

DOE PAGES

Ma, Jie; Liu, Zhen-Fei; Neaton, Jeffrey B.; ...

2016-06-30

We apply a recently developed Wannier-Koopmans method (WKM), based on density functional theory (DFT), to calculate the electronic energy level alignment at an interface between a molecule and metal substrate. We consider two systems: benzenediamine on Au (111), and a bipyridine-Au molecular junction. The WKM calculated level alignment agrees well with the experimental measurements where available, as well as previous GW and DFT + Σ results. These results suggest that the WKM is a general approach that can be used to correct DFT eigenvalue errors, not only in bulk semiconductors and isolated molecules, but also in hybrid interfaces.

Observation of rotational revivals for iodine molecules in helium droplets using a near-adiabatic laser pulse

NASA Astrophysics Data System (ADS)

Shepperson, Benjamin; Chatterley, Adam S.; Christiansen, Lars; Søndergaard, Anders A.; Stapelfeldt, Henrik

2018-01-01

A 160-ps near-Gaussian, linearly polarized laser pulse is used to align iodine (I2) molecules embedded in helium nanodroplets. The rise time of the laser pulse is sufficiently long and smooth that the alignment, characterized by , behaves adiabatically during the pulse turnon. However, after the laser pulse has turned off stays above 0.50 and a recurrence structure occurs ˜650 ps later. Measurements on isolated (I2) molecules with identical laser pulses are used to identify, through analysis of the observed half- and full-rotational revivals, that the nonadiabatic postpulse alignment dynamics results from a mild truncation of the trailing edge of the laser pulse. This truncation establishes a well-defined starting time for coherent rotation, which leads to the revival structures observed both for isolated molecules and molecules in He droplets. In the latter case the time-dependent trace recorded here is compared to that obtained previously for a 450-fs alignment pulse. It is found that the observed revivals are very similar.

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.

Application of Raman spectroscopy technology to studying Sudan I

NASA Astrophysics Data System (ADS)

Li, Gang; Zhang, Guoping; Chen, Chen

2006-06-01

Being an industrial dye, the Sudan I may have a toxic effect after oral intake on the body, and has recently been shown to cause cancer in rats, mice and rabbits. Because China and some other countries have detected the Sudan I in samples of the hot chilli powder and the chilli products, it is necessary to study the characteristics of this dye. As one kind of molecule scattering spectroscopy, Raman spectroscopy is characterized by the frequency excursion caused by interactions of molecules and photons. The frequency excursion reflects the margin between certain two vibrational or rotational energy states, and shows the information of the molecule. Because Raman spectroscopy can provides quick, easy, reproducible, and non-destructive analysis, both qualitative and quantitative, with no sample preparation required, Raman spectroscopy has been a particularly promising technique for analyzing the characteristics and structures of molecules, especially organic ones. Now, it has a broad application in biological, chemical, environmental and industrial applications. This paper firstly introduces Sudan I dye and the Raman spectroscopy technology, and then describes its application to the Sudan I. Secondly, the fingerprint spectra of the Sudan I are respectively assigned and analyzed in detail. Finally, the conclusion that the Raman spectroscopy technology is a powerful tool to determine the Sudan I is drawn.

Influence of silver nanoparticles on relaxation processes and efficiency of dipole – dipole energy transfer between dye molecules in polymethylmethacrylate films

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

Bryukhanov, V V; Borkunov, R Yu; Tsarkov, M V

The fluorescence and phosphorescence of dyes in thin polymethylmethacrylate (PMMA) films in the presence of ablated silver nanoparticles has been investigated in a wide temperature range by methods of femtosecond and picosecond laser photoexcitation. The fluorescence and phosphorescence times, as well as spectral and kinetic characteristics of rhodamine 6G (R6G) molecules in PMMA films are measured in a temperature range of 80 – 330 K. The temperature quenching activation energy of the fluorescence of R6G molecules in the presence of ablated silver nanoparticles is found. The vibrational relaxation rate of R6G in PMMA films is estimated, the efficiency of themore » dipole – dipole electron energy transfer between R6G and brilliant green molecules (enhanced by plasmonic interaction with ablated silver nanoparticles) is analysed, and the constants of this energy transfer are determined. (nanophotonics)« less

Hyperfine-Structure-Induced Depolarization of Impulsively Aligned I2 Molecules

NASA Astrophysics Data System (ADS)

Thomas, Esben F.; Søndergaard, Anders A.; Shepperson, Benjamin; Henriksen, Niels E.; Stapelfeldt, Henrik

2018-04-01

A moderately intense 450 fs laser pulse is used to create rotational wave packets in gas phase I2 molecules. The ensuing time-dependent alignment, measured by Coulomb explosion imaging with a delayed probe pulse, exhibits the characteristic revival structures expected for rotational wave packets but also a complex nonperiodic substructure and decreasing mean alignment not observed before. A quantum mechanical model attributes the phenomena to coupling between the rotational angular momenta and the nuclear spins through the electric quadrupole interaction. The calculated alignment trace agrees very well with the experimental results.

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

Kuz'mina, L. G., E-mail: kuzmina@igic.ras.ru; Vedernikov, A. I.; Sazonov, S. K.

The crystal packing of a number of styryl dyes of the pyridine series is analyzed. The structures of three dyes and three [2 + 2] photocycloaddition (PCA) products, 1,2,3,4-tetrasubstituted cyclobutanes, obtained in single crystals are determined by X-ray diffraction. Stacks of planar organic cations are characteristic of styryl dye packings. The proceeding of the PCA reaction as a single crystal-to-single crystal transformation in the syn head-to-head stacks is in principle impossible. The syn head-to-tail stacking packings are favorable for the PCA reactions resulting in the centrosymmetric rctt isomers of cyclobutane. The stacking packings, in which molecules are related by themore » twofold axes (the anti arrangement of molecules), are also favorable for PCA in single crystals. In this case, the products are the rtct isomers of cyclobutane. The presence of the I{sup -} counterions in a packing is a factor impeding the PCA reaction, because the secondary I-H-C bonds increase the rigidity of the crystal lattice. The conditions necessary for proceeding the PCA reactions in styryl dyes as single crystal-to-single crystal processes are as follows: (1) the stacks split into pairs of organic cations (dimers) with the d distances within 4.2 A in a dimer and d exceeding 4.2 A between the dimers; and (2) the dimers are surrounded by flexible shells consisting of anions, solvate molecules, or flexible moieties of the organic cations themselves.« less

Formic acid enhanced effective degradation of methyl orange dye in aqueous solutions under UV-Vis irradiation.

PubMed

Wang, Jingjing; Bai, Renbi

2016-09-15

Developing efficient technologies to treat recalcitrant organic dye wastewater has long been of great research and practical interest. In this study, a small molecule, formic acid (FA), was applied as a process enhancer for the degradation of methyl orange (MO) dye as a model recalcitrant organic pollutant in aqueous solutions under the condition of UV-Vis light irradiation and air aeration at the ambient temperature of 25 °C. It was found that the decolouration of the dye solutions can be rapidly achieved, reducing the time, for example, from around 17.6 h without FA to mostly about less than 2 h with the presence of FA. The mineralization rate of MO dye reached as high as 81.8% in 1.5 h in the case of initial MO dye concentration at 25 mg L(-1), which is in contrast to nearly no mineralization of the MO dye for a similar system without the FA added. The study revealed that the generation of the H2O2 species in the system was enhanced and the produced OH radicals effectively contributed to the degradation of the MO dye. Process parameters such as the initial concentration of MO dye, FA dosage and solution pH were all found to have some effect on the degradation efficiency under the same condition of UV-Vis light irradiation and air aeration. The MO dye degradation performance was found to follow a first-order reaction rate to the MO dye concentration in most cases and there existed a positive correlation between the reaction rate constant and the initial FA concentration. Compared to the traditional H2O2/UV-Vis oxidation system, the use of FA as a process-enhancing agent can have the advantages of low cost, easy availability, and safe to use. The study hence demonstrates a promising approach to use a readily available small molecule of FA to enhance the degradation of recalcitrant organic pollutants, such as MO dye, especially for their pre-treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed

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

2004-08-01

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

Extension lifetime for dye-sensitized solar cells through multiple dye adsorption/desorption process

NASA Astrophysics Data System (ADS)

Chiang, Yi-Fang; Chen, Ruei-Tang; Shen, Po-Shen; Chen, Peter; Guo, Tzung-Fang

2013-03-01

In this study, we propose a novel concept of extending the lifetime of dye-sensitized solar cells (DSCs) and reducing the costs of re-conditioning DSCs by recycling the FTO/TiO2 substrates. The photovoltaic performances of DSCs using substrates with various cycles of dye uptake and rinse off history are tested. The results show that dye adsorption and Voc are significantly increased under multiple dye adsorption/desorption process and resulted in the improvement of power conversion efficiency. Moreover, the dyeing kinetics is faster after multiple recycling processes, which is favorable for the industrial application. With surface analysis and charge transport characteristics, we also demonstrate the optimal functionality of TiO2/dye interface for the improved Voc and efficiency. The results confirm that the improved performances are due to increased dye loading and dense packing of dye molecules. Our results are beneficial for the understanding on the extension of DSCs lifetime after long-term operation in the application of DSC modules. This approach may also be applied in the replacement of newly synthesized photosensitizes to the active cells.

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.

Optical nanoscopy with contact Mie-particles: Resolution analysis

NASA Astrophysics Data System (ADS)

Maslov, Alexey V.; Astratov, Vasily N.

2017-06-01

The theoretical limits of resolution available in microspherical nanoscopy are explored using incoherent point emitters in the air. The images are calculated using a two-dimensional model and solving the Maxwell equations which account for the wave effects on the sub-wavelength scale of the emitter-microsphere interaction. Based on our results, we propose to use small dielectric particles with diameters λ ≲ D ≲ 2 λ made of a high-refractive-index material n ˜2 for imaging sub-wavelength objects. It is shown that such particles form virtual images below and real images above them. At wavelengths of the Mie resonances, these images have slightly better than ˜λ/4 resolution that can be attributed to the image magnification in close proximity to the object and contributions of its near field. The resonant super-resolution imaging of various point-like objects, such as dye molecules, fluorophores, or nanoplasmonic particles, can be realized by using narrow bandpass optical filters spectrally aligned with the Mie resonances.

WAVELENGTH AND ALIGNMENT TESTS FOR CONFOCAL SPECTRAL IMAGING SYSTEMS

EPA Science Inventory

Confocal spectral imaging (CSI) microscope systems now on the market delineate multiple fluorescent proteins, labels, or dyes within biological specimens by performing spectral characterizations. However, we find that some CSI present inconsistent spectral profiles of reference s...

Homebuilt single-molecule scanning confocal fluorescence microscope studies of single DNA/protein interactions.

PubMed

Zheng, Haocheng; Goldner, Lori S; Leuba, Sanford H

2007-03-01

Many technical improvements in fluorescence microscopy over the years have focused on decreasing background and increasing the signal to noise ratio (SNR). The scanning confocal fluorescence microscope (SCFM) represented a major improvement in these efforts. The SCFM acquires signal from a thin layer of a thick sample, rejecting light whose origin is not in the focal plane thereby dramatically decreasing the background signal. A second major innovation was the advent of high quantum-yield, low noise, single-photon counting detectors. The superior background rejection of SCFM combined with low-noise, high-yield detectors makes it possible to detect the fluorescence from single-dye molecules. By labeling a DNA molecule or a DNA/protein complex with a donor/acceptor dye pair, fluorescence resonance energy transfer (FRET) can be used to track conformational changes in the molecule/complex itself, on a single molecule/complex basis. In this methods paper, we describe the core concepts of SCFM in the context of a study that uses FRET to reveal conformational fluctuations in individual Holliday junction DNA molecules and nucleosomal particles. We also discuss data processing methods for SCFM.

Reliable energy level alignment at physisorbed molecule-metal interfaces from density functional theory.

PubMed

Egger, David A; Liu, Zhen-Fei; Neaton, Jeffrey B; Kronik, Leeor

2015-04-08

A key quantity for molecule-metal interfaces is the energy level alignment of molecular electronic states with the metallic Fermi level. We develop and apply an efficient theoretical method, based on density functional theory (DFT) that can yield quantitatively accurate energy level alignment information for physisorbed metal-molecule interfaces. The method builds on the "DFT+Σ" approach, grounded in many-body perturbation theory, which introduces an approximate electron self-energy that corrects the level alignment obtained from conventional DFT for missing exchange and correlation effects associated with the gas-phase molecule and substrate polarization. Here, we extend the DFT+Σ approach in two important ways: first, we employ optimally tuned range-separated hybrid functionals to compute the gas-phase term, rather than rely on GW or total energy differences as in prior work; second, we use a nonclassical DFT-determined image-charge plane of the metallic surface to compute the substrate polarization term, rather than the classical DFT-derived image plane used previously. We validate this new approach by a detailed comparison with experimental and theoretical reference data for several prototypical molecule-metal interfaces, where excellent agreement with experiment is achieved: benzene on graphite (0001), and 1,4-benzenediamine, Cu-phthalocyanine, and 3,4,9,10-perylene-tetracarboxylic-dianhydride on Au(111). In particular, we show that the method correctly captures level alignment trends across chemical systems and that it retains its accuracy even for molecules for which conventional DFT suffers from severe self-interaction errors.

Proton-Induced Trap States, Injection and Recombination Dynamics in Water-Splitting Dye-Sensitized Photoelectrochemical Cells.

PubMed

McCool, Nicholas S; Swierk, John R; Nemes, Coleen T; Saunders, Timothy P; Schmuttenmaer, Charles A; Mallouk, Thomas E

2016-07-06

Water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) utilize a sensitized metal oxide and a water oxidation catalyst in order to generate hydrogen and oxygen from water. Although the Faradaic efficiency of water splitting is close to unity, the recombination of photogenerated electrons with oxidized dye molecules causes the quantum efficiency of these devices to be low. It is therefore important to understand recombination mechanisms in order to develop strategies to minimize them. In this paper, we discuss the role of proton intercalation in the formation of recombination centers. Proton intercalation forms nonmobile surface trap states that persist on time scales that are orders of magnitude longer than the electron lifetime in TiO2. As a result of electron trapping, recombination with surface-bound oxidized dye molecules occurs. We report a method for effectively removing the surface trap states by mildly heating the electrodes under vacuum, which appears to primarily improve the injection kinetics without affecting bulk trapping dynamics, further stressing the importance of proton control in WS-DSPECs.

A hydrophobic dye-encapsulated nano-hybrid as an efficient fluorescent probe for living cell imaging.

PubMed

Chang, Shu; Wu, Xumeng; Li, Yongsheng; Niu, Dechao; Ma, Zhi; Zhao, Wenru; Gu, Jinlou; Dong, Wenjie; Ding, Feng; Zhu, Weihong; Shi, Jianlin

2012-07-01

Water-soluble hydrophobic-dye@nano-hybrids (DPN@NHs) with extraordinarily enhanced fluorescent performance were fabricated by encapsulating the hydrophobic dye molecules into the core of the hybrid nanospheres based on the self-assembly of amphiphilic block copolymers followed by shell cross-linking using 3-mercaptopropyltrimethoxy-silane. The DPN@NHs are 50 nm in size, are monodispersed in aqueous solution and have a quantum yield enhanced by 30 times. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic studies of interactions between dyes and model molecules of Alzheimer's disease

NASA Astrophysics Data System (ADS)

Elhaddaoui, A.; Delacourte, A.; Turrell, S.

1993-06-01

Raman, FTIR, fluorescence, and UV-visible spectra are used to study interactions between amuloid-labelling dyes and poly-L-lysine and bovine insulin, two proteins which play the role of models of (beta) amyloid of Alzheimers disease. It is found that though the (beta) conformation of the peptide is not essential, it helps to encourage binding which appears to be stable and specific in nature, involving SO3- groups of the dyes and NH2 groups of the proteins.

M13 Virus based detection of Bacterial Infections in Living Hosts

PubMed Central

Bardhan, Neelkanth M.; Ghosh, Debadyuti; Belcher, Angela M.

2014-01-01

We report a first method for using M13 bacteriophage as a multifunctional scaffold for optically imaging bacterial infections in vivo. We demonstrate that M13 virus conjugated with hundreds of dye molecules (M13-Dye) can target and distinguish pathogenic infections of F-pili expressing and F-negative strains of E. coli. Further, in order to tune this M13-Dye complex suitable for targeting other strains of bacteria, we have used a 1-step reaction for creating an anti-bacterial antibody-M13-Dye probe. As an example, we show anti-S.aureus-M13-Dye able to target and image infections of S. aureus in living hosts, with a 3.7x increase in fluorescence over background. PMID:23576418

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.

Imaging chromatin nanostructure with binding-activated localization microscopy based on DNA structure fluctuations

PubMed Central

Szczurek, Aleksander; Klewes, Ludger; Xing, Jun; Gourram, Amine; Birk, Udo; Knecht, Hans; Dobrucki, Jurek W.; Mai, Sabine

2017-01-01

Abstract Advanced light microscopy is an important tool for nanostructure analysis of chromatin. In this report we present a general concept for Single Molecule localization Microscopy (SMLM) super-resolved imaging of DNA-binding dyes based on modifying the properties of DNA and the dye. By careful adjustment of the chemical environment leading to local, reversible DNA melting and hybridization control over the fluorescence signal of the DNA-binding dye molecules can be introduced. We postulate a transient binding as the basis for our variation of binding-activated localization microscopy (BALM). We demonstrate that several intercalating and minor-groove binding DNA dyes can be used to register (optically isolate) only a few DNA-binding dye signals at a time. To highlight this DNA structure fluctuation-assisted BALM (fBALM), we applied it to measure, for the first time, nanoscale differences in nuclear architecture in model ischemia with an anticipated structural resolution of approximately 50 nm. Our data suggest that this approach may open an avenue for the enhanced microscopic analysis of chromatin nano-architecture and hence the microscopic analysis of nuclear structure aberrations occurring in various pathological conditions. It may also become possible to analyse nuclear nanostructure differences in different cell types, stages of development or environmental stress conditions. PMID:28082388

Superresolution microscopy with transient binding.

PubMed

Molle, Julia; Raab, Mario; Holzmeister, Susanne; Schmitt-Monreal, Daniel; Grohmann, Dina; He, Zhike; Tinnefeld, Philip

2016-06-01

For single-molecule localization based superresolution, the concentration of fluorescent labels has to be thinned out. This is commonly achieved by photophysically or photochemically deactivating subsets of molecules. Alternatively, apparent switching of molecules can be achieved by transient binding of fluorescent labels. Here, a diffusing dye yields bright fluorescent spots when binding to the structure of interest. As the binding interaction is weak, the labeling is reversible and the dye ligand construct diffuses back into solution. This approach of achieving superresolution by transient binding (STB) is reviewed in this manuscript. Different realizations of STB are discussed and compared to other localization-based superresolution modalities. We propose the development of labeling strategies that will make STB a highly versatile tool for superresolution microscopy at highest resolution. Copyright © 2015 Elsevier Ltd. 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

Stimulated emission and optical properties of pyranyliden fragment containing compounds in PVK matrix

NASA Astrophysics Data System (ADS)

Vembris, Aivars; Zarins, Elmars; Kokars, Valdis

2017-10-01

Organic solid state lasers are thoughtfully investigated due to their potential applications in communication, sensors, biomedicine, etc. Low amplified spontaneous emission (ASE) excitation threshold value is essential for further use of the material in devices. Intramolecular interaction limits high molecule density load in the matrix. It is the case of the well-known red light emitting laser dye - 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM). The lowest ASE threshold value of the mentioned laser dye could be obtained within the concentration range between 2 and 4 wt%. At higher concentration threshold energy drastically increases. In this work optical and ASE properties of three original DCM derivatives in poly(N-vinylcarbazole) (PVK) at various concentrations will be discussed. One of the derivatives is modified DCM dye in which the methyl substituents in the electron donor part have been replaced with bulky trityloxyethyl groups (DWK-1). These sterically significant functional groups do not influence electron transitions in the dye but prevent aggregation of the molecules. The chemical structure of the second investigated compound is similar to DWK-1 where the methyl group is replaced with the tert-butyl substituent (DWK-1TB). The third derivative (DWK-2) consists of two N,N-di(trityloxyethyl)amino electron donor groups. All results were compared with DCM:PVK system. Photoluminescence quantum yield (PLQY) is up to ten times larger for DWK-1TB with respect to DCM systems. Bulky trityloxyethyl groups prevent aggregation of the molecules thus decreasing interaction between dyes and amount of non-radiative decays. The red shift of the photoluminescence and amplified spontaneous emission at higher concentrations were observed due to the solid state solvation effect. The increase of the investigated dye density in the matrix with a smaller reduction in PLQY resulted in low ASE threshold energy. The lowest threshold value was obtained around 21 μJ/cm2 (2.1 kW/cm2) in DWK-1TB:PVK films.

A luminescent Lanthanide-free MOF nanohybrid for highly sensitive ratiometric temperature sensing in physiological range.

PubMed

Zhou, You; Zhang, Denan; Zeng, Jin; Gan, Ning; Cuan, Jing

2018-05-01

Luminescent MOF materials with tunable emissions and energy/charge transfer processes have been extensively explored as ratiometric temperature sensors. However, most of the ratiometric MOF thermometers reported thus far are based on the MOFs containing photoactive lanthanides, which are potentially facing cost issue and serious supply shortage. Here, we present a ratiometric luminescent thermometer based on a dual-emitting lanthanide-free MOF hybrid, which is developed by encapsulation of a fluorescent dye into a robust nanocrystalline zirconium-based MOF through a one-pot synthesis approach. The structure and morphology of the hybrid product was characterized by Powder X-ray diffraction (PXRD), N 2 adsorption-desorption measurement and Scanning electron microscopy (SEM). The pore confinement effect well isolates the guest dye molecules and therefore suppresses the nonradiative energy transfer process between dye molecules. The incorporated dye emission is mainly sensitized by the organic linkers within MOF through fluorescence resonance energy transfer. The ratiometric luminescence of the MOF hybrid shows a significant response to temperature due to the thermal-related back energy transfer process from dye molecules and organic linkers, thus can be exploited for self-calibrated temperature sensing. The maximum thermometric sensitivity is 1.19% °C -1 in the physiological temperature range, which is among the highest for the ratiomtric MOF thermometers that operating in 25-45°C. The temperature resolution is better than 0.1°C over the entire operative range (20-60°C). By integrating the advantages of excellent stability, nanoscale nature, and high sensitivity and precision in the physiological temperature range, this dye@MOF hybrid might have potential application in biomedical diagnosis. What' more, this work has expanded the possibility of non-lanthanide luminescent MOF materials for the development of ratiometric temperature sensors. Copyright © 2018 Elsevier B.V. All rights reserved.

Localization microscopy of DNA in situ using Vybrant(®) DyeCycle™ Violet fluorescent probe: A new approach to study nuclear nanostructure at single molecule resolution.

PubMed

Żurek-Biesiada, Dominika; Szczurek, Aleksander T; Prakash, Kirti; Mohana, Giriram K; Lee, Hyun-Keun; Roignant, Jean-Yves; Birk, Udo J; Dobrucki, Jurek W; Cremer, Christoph

2016-05-01

Higher order chromatin structure is not only required to compact and spatially arrange long chromatids within a nucleus, but have also important functional roles, including control of gene expression and DNA processing. However, studies of chromatin nanostructures cannot be performed using conventional widefield and confocal microscopy because of the limited optical resolution. Various methods of superresolution microscopy have been described to overcome this difficulty, like structured illumination and single molecule localization microscopy. We report here that the standard DNA dye Vybrant(®) DyeCycle™ Violet can be used to provide single molecule localization microscopy (SMLM) images of DNA in nuclei of fixed mammalian cells. This SMLM method enabled optical isolation and localization of large numbers of DNA-bound molecules, usually in excess of 10(6) signals in one cell nucleus. The technique yielded high-quality images of nuclear DNA density, revealing subdiffraction chromatin structures of the size in the order of 100nm; the interchromatin compartment was visualized at unprecedented optical resolution. The approach offers several advantages over previously described high resolution DNA imaging methods, including high specificity, an ability to record images using a single wavelength excitation, and a higher density of single molecule signals than reported in previous SMLM studies. The method is compatible with DNA/multicolor SMLM imaging which employs simple staining methods suited also for conventional optical microscopy. Copyright © 2016. Published by Elsevier Inc.

Probabilistic biological network alignment.

PubMed

Todor, Andrei; Dobra, Alin; Kahveci, Tamer

2013-01-01

Interactions between molecules are probabilistic events. An interaction may or may not happen with some probability, depending on a variety of factors such as the size, abundance, or proximity of the interacting molecules. In this paper, we consider the problem of aligning two biological networks. Unlike existing methods, we allow one of the two networks to contain probabilistic interactions. Allowing interaction probabilities makes the alignment more biologically relevant at the expense of explosive growth in the number of alternative topologies that may arise from different subsets of interactions that take place. We develop a novel method that efficiently and precisely characterizes this massive search space. We represent the topological similarity between pairs of aligned molecules (i.e., proteins) with the help of random variables and compute their expected values. We validate our method showing that, without sacrificing the running time performance, it can produce novel alignments. Our results also demonstrate that our method identifies biologically meaningful mappings under a comprehensive set of criteria used in the literature as well as the statistical coherence measure that we developed to analyze the statistical significance of the similarity of the functions of the aligned protein pairs.

The energy level alignment at metal–molecule interfaces using Wannier–Koopmans method

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

Ma, Jie; Wang, Lin-Wang, E-mail: lwwang@lbl.gov; Liu, Zhen-Fei

2016-06-27

We apply a recently developed Wannier–Koopmans method (WKM), based on density functional theory (DFT), to calculate the electronic energy level alignment at an interface between a molecule and metal substrate. We consider two systems: benzenediamine on Au (111), and a bipyridine-Au molecular junction. The WKM calculated level alignment agrees well with the experimental measurements where available, as well as previous GW and DFT + Σ results. Our results suggest that the WKM is a general approach that can be used to correct DFT eigenvalue errors, not only in bulk semiconductors and isolated molecules, but also in hybrid interfaces.

Recent progress in reversible photodegradation of Disperse Orange 11 when doped in PMMA

NASA Astrophysics Data System (ADS)

Ramini, Shiva K.; Anderson, Benjamin; Kuzyk, Mark G.

2011-12-01

We report observations that dye-doped PMMA polymer with the organic dye Disperse Orange 11 exhibits self healing after photodegradation by continuous optical pumping whereas in liquid solution, degradation is permanent. This observation illustrates the important role of the polymer matrix in facilitating recovery of the dye molecules. In this work, we report on linear optical absorbance studies that confirm the existence of a quasi-stable state that is not formed in liquid solution. Studies as a function of dye concentration and temperature support our hypothesis of the role of molecular interactions in the decay and healing process that is mediated by the polymer host.

Energy transfer dynamics from individual semiconductor nanoantennae to dye molecules with implication to light-harvesting nanosystems

NASA Astrophysics Data System (ADS)

Shan, Guangcun; Hu, Mingjun; Yan, Ze; Li, Xin; Huang, Wei

2018-03-01

Semiconductor nanocrystals can be used as nanoscale optical antennae to photoexcite individual dye molecules in an ensemble via energy transfer mechanism. The theoretical framework developed by Förster and others describes how electronic excitation migrates in the photosynthetic apparatus of plants, algae, and bacteria from light absorbing pigments to reaction centers where light energy is utilized for the eventual conversion into chemical energy. Herein we investigate the effect of the average donor-acceptor spacing on the time-resolved fluorescence intensity and dynamics of single donor-acceptor pairs with the dye acceptor concentration decreasing by using quantum Monte-Carlo simulation of FRET dynamics. Our results validated that the spatial disorder controlling the microscopic energy transfer rates accounts for the scatter in donor fluorescence lifetimes and intensities, which provides a new design guideline for artificial light-harvesting nanosystems.

Encapsulation of porphyrins and chlorins in biodegradable nanoparticles: the effect of dye lipophilicity on the extravasation and the photothrombic activity. A comparative study.

PubMed

Pegaz, Bernadette; Debefve, Elodie; Borle, Francois; Ballini, Jean-Pierre; van den Bergh, Hubert; Kouakou-Konan, Yvette Niamien

2005-07-01

In the present work, we performed a preclinical inter-comparison study using several photosensitizers with the goal of optimizing photodynamic therapy (PDT) for the treatment of choroidal neovascularization (CNV) associated with age-related macular degeneration. The tested molecules were the porphyrins meso-tetraphenylporphyrin (TPP) and meso-tetra-(4-carboxyphenyl)-porphyrin (TCPP), and the chlorins pheophorbide-a (Pheo-a) and chlorin e(6) (Ce(6)). Each of these molecules was entrapped in biodegradable nanoparticles (NP) based on poly(d,l-lactic acid). The influence of the degree of lipophilicity on the incorporation efficiency of the drug in the NPs, and on the dye leakage from blood vessels as well as on the photothrombic efficiency was investigated using the chick chorioallantoic membrane (CAM) as in vivo model. NP characterization showed that the dye was more effectively entrapped in the polymeric matrix when its degree of lipophilicity increased. While less lipophilic compounds (TCPP, Ce(6)) extravasate rather easily, the more lipophilic dyes (TPP, Pheo-a) tend to remain inside the blood vessels. After injection of a drug dose of 1 mg/kg body weight and a drug-light application interval of 1 min, irradiation with light doses ranging from 5 to 20 J/cm(2) led to the highest photothrombic efficiency when using the NPs loaded with the most lipophilic molecule (TPP). The latter induced vascular damage, which was significantly higher than that observed with the other molecules tested. Thus, in addition to minimal leakage from blood vessels, the TPP in NP formulation exhibited photothrombic efficiency similar to Visudyne which was also tested in the CAM model.

Liquid crystal point diffraction interferometer. Ph.D. Thesis - Arizona Univ., 1995

NASA Technical Reports Server (NTRS)

Mercer, Carolyn R.

1995-01-01

A new instrument, the liquid crystal point diffraction-interferometer (LCPDI), has been developed for the measurement of phase objects. This instrument maintains the compact, robust design of Linnik's point diffraction interferometer (PDI) and adds to it phase stepping capability for quantitative interferogram analysis. The result is a compact, simple to align, environmentally insensitive interferometer capable of accurately measuring optical wavefronts with very high data density and with automated data reduction. This dissertation describes the theory of both the PDI and liquid crystal phase control. The design considerations for the LCPDI are presented, including manufacturing considerations. The operation and performance of the LCPDI are discussed, including sections regarding alignment, calibration, and amplitude modulation effects. The LCPDI is then demonstrated using two phase objects: defocus difference wavefront, and a temperature distribution across a heated chamber filled with silicone oil. The measured results are compared to theoretical or independently measured results and show excellent agreement. A computer simulation of the LCPDI was performed to verify the source of observed periodic phase measurement error. The error stems from intensity variations caused by dye molecules rotating within the liquid crystal layer. Methods are discussed for reducing this error. Algorithms are presented which reduce this error; they are also useful for any phase-stepping interferometer that has unwanted intensity fluctuations, such as those caused by unregulated lasers.

Growth of potassium sulfate crystals in the presence of organic dyes: in situ characterization by atomic force microscopy

NASA Astrophysics Data System (ADS)

Mauri, Andrea; Moret, Massimo

2000-01-01

In situ atomic force microscopy (AFM) has been used to observe potassium sulfate crystals growing in the presence of acid fuchsin and pyranine. These polysulfonated dyes are well known for their ability to adsorb onto the {1 1 0} and {0 1 0} (pyranine only) crystal faces. Using AFM, we analyzed the changes in surface micromorphology induced by the additives on advancing steps for the {1 1 0} and {0 1 0} surfaces. In situ AFM showed that layers grow by step flow at pre-existing steps by the addition of growth units at the step edges. It has been found that dye concentrations as low as ˜2×10 -6 M for pyranine and ˜4×10 -4 M for acid fuchsin produce significant changes in the step morphology and growth rates. The additive molecules attach to the terraces and pin the growing front. As a consequence, the edges of the growing steps become jagged as the dye molecules are adsorbed onto the crystal surface. At critical dye concentrations crystal growth is heavily hampered or even stopped along certain crystallographic directions producing, on a macroscopic scale, strong habit modifications. The formation of dye inclusions by means of macrosteps overgrowing the poisoned surface was also imaged. Interestingly, comparison of the in situ AFM experiments with previous habit modification studies showed acid fuchsin is also able to enter the {0 1 0} surfaces, a previously unnoticed phenomenon.

Coherent control of molecular alignment of homonuclear diatomic molecules by analytically designed laser pulses.

PubMed

Zou, Shiyang; Sanz, Cristina; Balint-Kurti, Gabriel G

2008-09-28

We present an analytic scheme for designing laser pulses to manipulate the field-free molecular alignment of a homonuclear diatomic molecule. The scheme is based on the use of a generalized pulse-area theorem and makes use of pulses constructed around two-photon resonant frequencies. In the proposed scheme, the populations and relative phases of the rovibrational states of the molecule are independently controlled utilizing changes in the laser intensity and in the carrier-envelope phase difference, respectively. This allows us to create the correct coherent superposition of rovibrational states needed to achieve optimal molecular alignment. The validity and efficiency of the scheme are demonstrated by explicit application to the H(2) molecule. The analytically designed laser pulses are tested by exact numerical solutions of the time-dependent Schrodinger equation including laser-molecule interactions to all orders of the field strength. The design of a sequence of pulses to further enhance molecular alignment is also discussed and tested. It is found that the rotating wave approximation used in the analytic design of the laser pulses leads to small errors in the prediction of the relative phase of the rotational states. It is further shown how these errors may be easily corrected.

XUV ionization of aligned molecules

NASA Astrophysics Data System (ADS)

Kelkensberg, F.; Rouzée, A.; Siu, W.; Gademann, G.; Johnsson, P.; Lucchini, M.; Lucchese, R. R.; Vrakking, M. J. J.

2011-11-01

New extreme-ultraviolet (XUV) light sources such as high-order-harmonic generation (HHG) and free-electron lasers (FELs), combined with laser-induced alignment techniques, enable novel methods for making molecular movies based on measuring molecular frame photoelectron angular distributions. Experiments are presented where CO2 molecules were impulsively aligned using a near-infrared laser and ionized using femtosecond XUV pulses obtained by HHG. Measured electron angular distributions reveal contributions from four orbitals and the onset of the influence of the molecular structure.

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

Dye-ligand affinity systems.

PubMed

Denizli, A; Pişkin, E

2001-10-30

Dye-ligands have been considered as one of the important alternatives to natural counterparts for specific affinity chromatography. Dye-ligands are able to bind most types of proteins, in some cases in a remarkably specific manner. They are commercially available, inexpensive, and can easily be immobilized, especially on matrices bearing hydroxyl groups. Although dyes are all synthetic in nature, they are still classified as affinity ligands because they interact with the active sites of many proteins mimicking the structure of the substrates, cofactors, or binding agents for those proteins. A number of textile dyes, known as reactive dyes, have been used for protein purification. Most of these reactive dyes consist of a chromophore (either azo dyes, anthraquinone, or phathalocyanine), linked to a reactive group (often a mono- or dichlorotriazine ring). The interaction between the dye ligand and proteins can be by complex combination of electrostatic, hydrophobic, hydrogen bonding. Selection of the supporting matrix is the first important consideration in dye-affinity systems. There are several methods for immobilization of dye molecules onto the support matrix, in which usually several intermediate steps are followed. Both the adsorption and elution steps should carefully be optimized/designed for a successful separation. Dye-affinity systems in the form of spherical sorbents or as affinity membranes have been used in protein separation.

Direct Analysis of Textile Fabrics and Dyes Using IR Matrix-Assisted Laser Desorption Electrospray Ionization (MALDESI) Mass Spectrometry

PubMed Central

Cochran, Kristin H.; Barry, Jeremy A.; Muddiman, David C.; Hinks, David

2012-01-01

The forensic analysis of textile fibers uses a variety of techniques from microscopy to spectroscopy. One such technique that is often used to identify the dye(s) within the fiber is mass spectrometry (MS). In the traditional MS method, the dye must be extracted from the fabric and the dye components are separated by chromatography prior to mass spectrometric analysis. Direct analysis of the dye from the fabric allows the omission of the lengthy sample preparation involved in extraction, thereby significantly reducing the overall analysis time. Herein, a direct analysis of dyed textile fabric was performed using the infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) source for MS. In MALDESI, an IR laser with wavelength tuned to 2.94 μm is used to desorb the dye from the fabric sample with the aid of water as the matrix. The desorbed dye molecules are then post-ionized by electrospray ionization (ESI). A variety of dye classes were analyzed from various fabrics with little to no sample preparation allowing for the identification of the dye mass and in some cases the fiber polymer. Those dyes that were not detected using MALDESI were also not observed by direct infusion ESI of the dye standard. PMID:23237031

Assessment of the banana pseudostem as a low-cost biosorbent for the removal of reactive blue 5G dye.

PubMed

Módenes, Aparecido N; Espinoza-Quiñones, Fernando R; Geraldi, Claudinéia A Q; Manenti, Diego R; Trigueros, Daniela E G; Oliveira, Ana Paula de; Borba, Carlos E; Kroumov, Alexander D

2015-01-01

In this work, the removal of reactive blue 5G (RB5G) dye using the drying biomass of banana pseudostem (BPS) was investigated. The characterization of BPS particles was performed. Improvement in the RB5G dye removal performance at the following sorption conditions was evidenced: pH 1, 30°C sorption temperature and 40 rpm shaking, regardless of the particle size range. Kinetic RB5G dye sorption data obtained at better conditions fit well in an Elovich model. A combined Langmuir-BET isotherm model provides a good representation of the RB5G dye equilibrium sorption data, which shows the evidence of a physical sorption process on the BPS surface. Based on the results, the removal of RB5G dye molecules by BPS is based on a physical sorption process.

Process of changing the refractive index of a composite containing a polymer and a compound having large dipole moment and polarizability and applications thereof

NASA Technical Reports Server (NTRS)

Peyghambarian, Nasser (Inventor); Hendrickx, Eric (Inventor); Volodin, Boris (Inventor); Marder, Seth R. (Inventor); Kippelen, Bernard (Inventor)

2000-01-01

Fused ring bridge, ring locked dyes that form thermally stable photorfractive 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.

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.

A new probe using hybrid virus-dye nanoparticles for near-infrared fluorescence tomography

NASA Astrophysics Data System (ADS)

Wu, Changfeng; Barnhill, Hannah; Liang, Xiaoping; Wang, Qian; Jiang, Huabei

2005-11-01

A fluorescent probe based on bionanoparticle cowpea mosaic virus has been developed for near-infrared fluorescence tomography. A unique advantage of this probe is that over 30 dye molecules can be loaded onto each viral nanoparticle with an average diameter of 30 nm, making high local dye concentration (∼1.8 mM) possible without significant fluorescence quenching. This ability of high loading of local dye concentration would increase the signal-to-noise ratio considerably, thus sensitivity for detection. We demonstrate successful tomographic fluorescence imaging of a target containing the virus-dye nanoparticles embedded in a tissue-like phantom. Tomographic fluorescence data were obtained through a multi-channel frequency-domain system and the spatial maps of fluorescence quantum yield were recovered with a finite-element-based reconstruction algorithm.

M13 virus based detection of bacterial infections in living hosts.

PubMed

Bardhan, Neelkanth M; Ghosh, Debadyuti; Belcher, Angela M

2014-08-01

We report a first method for using M13 bacteriophage as a multifunctional scaffold for optically imaging bacterial infections in vivo. We demonstrate that M13 virus conjugated with hundreds of dye molecules (M13-Dye) can target and distinguish pathogenic infections of F-pili expressing and F-negative strains of E. coli. Further, in order to tune this M13-Dye complex suitable for targeting other strains of bacteria, we have used a 1-step reaction for creating an anti-bacterial antibody-M13-Dye probe. As an example, we show anti-S. aureus-M13-Dye able to target and image infections of S. aureus in living hosts, with a 3.7× increase in fluorescence over background. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On-chip tunable optofluidic dye laser

NASA Astrophysics Data System (ADS)

Cai, Zengyan; Shen, Zhenhua; Liu, Haigang; Yue, Huan; Zou, Yun; Chen, Xianfeng

2016-11-01

We demonstrate a chip-scale tunable optofluidic dye laser with Au-coated fibers as microcavity. The chip is fabricated by soft lithography. When the active region is pumped, a relatively low threshold of 6.7 μJ/mm2 is realized with multimode emission due to good confinement of the cavity mirrors, long active region, as well as total reflectivity. It is easy to tune the lasing emission wavelength by changing the solvent of laser dye. In addition, the various intensity ratios of multicolor lasing can be achieved by controlling flow rates of two fluid streams carried with different dye molecules. Furthermore, the convenience in fabrication and directional lasing emission outcoupled by the fiber make the tunable optofluidic dye laser a promising underlying coherent light source in the integrated optofluidic systems.

Preparation of K-doped TiO2 nanostructures by wet corrosion and their sunlight-driven photocatalytic performance

NASA Astrophysics Data System (ADS)

Shin, Eunhye; Jin, Saera; Kim, Jiyoon; Chang, Sung-Jin; Jun, Byung-Hyuk; Park, Kwang-Won; Hong, Jongin

2016-08-01

K-doped TiO2 nanowire networks were prepared by the corrosion reaction of Ti nanoparticles in an alkaline (potassium hydroxide: KOH) solution. The prepared nanostructures were characterized by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) analysis, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, X-ray diffraction (XRD) and photoluminescence (PL) spectra. Their sunlight-driven photocatalytic activity was also investigated with differently charged dye molecules, such as methylene blue, rhodamine B and methyl orange. The adsorption of the dye molecules on the photocatalyst surface would play a critical role in their selective photodegradation under sunlight illumination.

Modeling the color of natural dyes

NASA Astrophysics Data System (ADS)

Ge, Xiaochuan; Calzolari, Arrigo; Binnie, Simon; Baroni, Stefano

2013-03-01

We report on a theoretical study, based on time-dependent density-functional theory, of various factors affecting the optical properties of a few representative anthocyanins, a class of molecules responsible for the color of many fruits, flowers, and leaves, which have also aroused some interest for photovoltaic applications. We first address the influence of substituting different side groups in the phenyl ring of flavylium dyes. We find that these dyes can be classified into three broad classes, according to the number of peaks (1, 2, or 3) featured in the visible range, and give a rationale to this finding. We then examine the effects of solvent-induced thermal fluctuations and dielectric screening, by calculating the spectrum of a representative molecule in solution, for each one these classes. This is achieved by first running an ab initio molecular dynamics simulation of an explicit model for the water-solvated molecule, and then accumulating time averages of the optical spectra calculated on the fly. The effects of thermal fluctuations are shown to overshadow those of dielectric screening, and more dramatic the larger the number of peaks in the gas phase. The effects of different functionals (GGA vs. hybrids) on the calculated spectra are also addressed.

Computer simulation of gene detection without PCR by single molecule detection

NASA Astrophysics Data System (ADS)

Davis, Lloyd M.; Williams, John G.; Lamb, Don T.

1999-01-01

Pioneer Hi-Bred is developing a low-cost method for rapid screening of DNA, for use in research on elite crop seed genetics. Unamplified genomic DNA with the requisite base sequence is simultaneously labeled by two different colored fluorescent probes, which hybridize near the selected gene. Dual-channel single molecule detection (SMD) within a flow cell, then provides a sensitive and specific assay for the gene. The technique has been demonstrated using frequency- doubled Nd:YAG laser excitation of two visible-wavelength dyes. A prototype instrument employing infrared fluorophores and laser diodes for excitation has been developed. Here, we report results from a Monte Carlo simulation of the new instrument, in which experimentally determined photophysical parameters for candidate infrared dyes are used for parametric studies of experimental operating conditions. Fluorophore photostability is found to be a key factor in determining the instrument sensitivity. Most infrared dyes have poor photostability, resulting in inefficient SMD. However, the normalized cross-correlation function of the photon signals from each of the two channels can still yield a discernable peak, provided that the concentration of dual- labeled molecules is sufficiently high. Further, for low concentrations, processing of the two photon streams with Gaussian -weighted sliding sum digital filters and selection of simultaneously occurring peaks can also provide a sensitive indicator of the presence of dual-labeled molecules, although accidental coincidences must be considered in the interpretation of results.

Enhancing the Sensitivity of DNA Microarray Using Dye-Doped Silica Nanoparticles: Detection of Human Papilloma Virus

NASA Astrophysics Data System (ADS)

Enrichi, F.; Riccò, R.; Meneghello, A.; Pierobon, R.; Canton, G.; Cretaio, E.

2010-10-01

DNA microarray is a high-throughput technology used for detection and quantification of nucleic acid molecules and others of biological interest. The analysis is based on the specific hybridization between probe sequences deposited in array and a target ss-DNA amplified by PCR and functionalized by a fluorescent dye. Organic labels have well known disadvantages like photobleaching and low signal intensities, which put a limitation to the lower amount of DNA material that can be detected. Therefore for trace analysis the development of more efficient biomarkers is required. With this aim we present in this paper the synthesis and application of alternative hybrid nanosystems obtained by incorporating standard fluorescent molecules into monodisperse silica nanoparticles. Efficient application to the detection of Human Papilloma Virus is demonstrated. This virus is associated to the formation of cervical cancer, a leading cause of death by cancer for women worldwide. It is shown that the use of the novel biomarkers increases the optical signal of about one order of magnitude with respect to the free dyes or quantum dots in conventional instruments. This is due to the high number of molecules that can be accommodated into each nanoparticle, to the reduced photobleaching and to the improved environmental protection of the dyes when encapsulated in the silica matrix. The cheap and easy synthesis of these luminescent particles, the stability in water, the surface functionalizability and bio-compatibility make them very promising for present and future bio-labeling and bio-imaging applications.

Reading Out Single-Molecule Digital RNA and DNA Isothermal Amplification in Nanoliter Volumes with Unmodified Camera Phones

PubMed Central

2016-01-01

Digital single-molecule technologies are expanding diagnostic capabilities, enabling the ultrasensitive quantification of targets, such as viral load in HIV and hepatitis C infections, by directly counting single molecules. Replacing fluorescent readout with a robust visual readout that can be captured by any unmodified cell phone camera will facilitate the global distribution of diagnostic tests, including in limited-resource settings where the need is greatest. This paper describes a methodology for developing a visual readout system for digital single-molecule amplification of RNA and DNA by (i) selecting colorimetric amplification-indicator dyes that are compatible with the spectral sensitivity of standard mobile phones, and (ii) identifying an optimal ratiometric image-process for a selected dye to achieve a readout that is robust to lighting conditions and camera hardware and provides unambiguous quantitative results, even for colorblind users. We also include an analysis of the limitations of this methodology, and provide a microfluidic approach that can be applied to expand dynamic range and improve reaction performance, allowing ultrasensitive, quantitative measurements at volumes as low as 5 nL. We validate this methodology using SlipChip-based digital single-molecule isothermal amplification with λDNA as a model and hepatitis C viral RNA as a clinically relevant target. The innovative combination of isothermal amplification chemistry in the presence of a judiciously chosen indicator dye and ratiometric image processing with SlipChip technology allowed the sequence-specific visual readout of single nucleic acid molecules in nanoliter volumes with an unmodified cell phone camera. When paired with devices that integrate sample preparation and nucleic acid amplification, this hardware-agnostic approach will increase the affordability and the distribution of quantitative diagnostic and environmental tests. PMID:26900709

Solar light induced and TiO2 assisted degradation of textile dye reactive blue 4.

PubMed

Neppolian, B; Choi, H C; Sakthivel, S; Arabindoo, B; Murugesan, V

2002-03-01

Aqueous solutions of reactive blue 4 textile dye are totally mineralised when irradiated with TiO2 photocatalyst. A solution containing 4 x 10(-4) M dye was completely degraded in 24 h irradiation time. The intensity of the solar light was measured using Lux meter. The results showed that the dye molecules were completely degraded to CO2, SO4(2-), NO3-, NH4+ and H2O under solar irradiation. The addition of hydrogen peroxide and potassium persulphate influenced the photodegradation efficiency. The rapidity of photodegradation of dye intermediates were observed in the presence of hydrogen peroxide than in its absence. The auxiliary chemicals such as sodium carbonate and sodium chloride substantially affected the photodegradation efficiency. High performance liquid chromatography and chemical oxygen demand were used to study the mineralisation and degradation of the dye respectively. It is concluded that solar light induced degradation of textile dye in wastewater is a viable technique for wastewater treatment.

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.

Applications of Fluorogens with Rotor Structures in Solar Cells.

PubMed

Ong, Kok-Haw; Liu, Bin

2017-05-29

Solar cells are devices that convert light energy into electricity. To drive greater adoption of solar cell technologies, higher cell efficiencies and reductions in manufacturing cost are necessary. Fluorogens containing rotor structures may be helpful in addressing some of these challenges due to their unique twisted structures and photophysics. In this review, we discuss the applications of rotor-containing molecules as dyes for luminescent down-shifting layers and luminescent solar concentrators, where their aggregation-induced emission properties and large Stokes shifts are highly desirable. We also discuss the applications of molecules containing rotors in third-generation solar cell technologies, namely dye-sensitized solar cells and organic photovoltaics, where the twisted 3-dimensional rotor structures are used primarily for aggregation control. Finally, we discuss perspectives on the future role of molecules containing rotor structures in solar cell technologies.

DNA Origami Directed Au Nanostar Dimers for Single-Molecule Surface-Enhanced Raman Scattering.

PubMed

Tanwar, Swati; Haldar, Krishna Kanta; Sen, Tapasi

2017-12-06

We demonstrate the synthesis of Au nanostar dimers with tunable interparticle gap and controlled stoichiometry assembled on DNA origami. Au nanostars with uniform and sharp tips were immobilized on rectangular DNA origami dimerized structures to create nanoantennas containing monomeric and dimeric Au nanostars. Single Texas red (TR) dye was specifically attached in the junction of the dimerized origami to act as a Raman reporter molecule. The SERS enhancement factors of single TR dye molecules located in the conjunction region in dimer structures having interparticle gaps of 7 and 13 nm are 2 × 10 10 and 8 × 10 9 , respectively, which are strong enough for single analyte detection. The highly enhanced electromagnetic field generated by the plasmon coupling between sharp tips and cores of two Au nanostars in the wide conjunction region allows the accommodation and specific detection of large biomolecules. Such DNA-directed assembled nanoantennas with controlled interparticle separation distance and stoichiometry, and well-defined geometry, can be used as excellent substrates in single-molecule SERS spectroscopy and will have potential applications as a reproducible platform in single-molecule sensing.

XUV ionization of aligned molecules

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

Kelkensberg, F.; Siu, W.; Gademann, G.

2011-11-15

New extreme-ultraviolet (XUV) light sources such as high-order-harmonic generation (HHG) and free-electron lasers (FELs), combined with laser-induced alignment techniques, enable novel methods for making molecular movies based on measuring molecular frame photoelectron angular distributions. Experiments are presented where CO{sub 2} molecules were impulsively aligned using a near-infrared laser and ionized using femtosecond XUV pulses obtained by HHG. Measured electron angular distributions reveal contributions from four orbitals and the onset of the influence of the molecular structure.

Fabrication and characterization of dichroic fine crystals by the reprecipitation method

NASA Astrophysics Data System (ADS)

Iino, Tatsuya; Mori, Shunsuke; Shito, Keiji; Kimura, Ayaka; Morishita, Yoshii; Chiba, Takayuki; Katagiri, Hiroshi; Okada, Shuji; Masuhara, Akito

2018-06-01

Suspended particle devices can rapidly switch from a dark blue state to a clear state by applying AC voltage, but their maximum transmittance has to be improved. In this work, we have targeted dichroic dyes and applied the reprecipitation method to KPD-503, a trisazo dye showing little dichroism in bulk crystals despite the dye molecules having large dichroism. As a result, microcrystals showing large dichroism were obtained. These microcrystals were considered to have a kinetically stable structure and oriented by voltage in a dispersing medium.

High conversion efficiency distributed feedback laser from a dye-doped holographic transmission grating

NASA Astrophysics Data System (ADS)

Liu, Lijuan; Zhang, Guiyang; Kong, Xiaobo; Liu, Yonggang; Xuan, Li

2018-01-01

A high conversion efficiency distributed feedback (DFB) laser from a dye-doped holographic polymer dispersed liquid crystal (HPDLC) transmission grating structure was reported. The alignment polyimide (PI) films were used to control the orientation of the phase separated liquid crystals (LCs) to increase the refractive index difference between the LC and the polymer, so it can provide better light feedback. The lasing wavelength located at 645.8 nm near the maximum of the amplified spontaneous emission (ASE) spectrum with the lowest threshold 0.97 μ J/pulse and the highest conversion efficiency 1.6% was obtained. The laser performance under electric field were also investigated and illustrated. The simple configuration, one-step fabrication organic dye laser shows the potential to realize ultra-low cost plastic lasers.

Use of dye to distinguish salt and protein crystals under microcrystallization conditions

NASA Technical Reports Server (NTRS)

Cosenza, Larry (Inventor); Gester, Thomas E. (Inventor); Bray, Terry L. (Inventor); DeLucas, Lawrence J. (Inventor); Hamrick, David T. (Inventor)

2007-01-01

An improved method of screening crystal growth conditions is provided wherein molecules are crystallized from solutions containing dyes. These dyes are selectively incorporated or associated with crystals of particular character thereby rendering crystals of particular character colored and improving detection of the dyed crystals. A preferred method involves use of dyes in protein solutions overlayed by oil. Use of oil allows the use of small volumes of solution and facilitates the screening of large numbers of crystallization conditions in arrays using automated devices that dispense appropriate solutions to generate crystallization trials, overlay crystallization trials with an oil, provide appropriate conditions conducive to crystallization and enhance detection of dyed (colored) or undyed (uncolored) crystals that result.

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

A general nuclear magnetic resonance analysis of hetero-association of aromatic molecules in aqueous solution

NASA Astrophysics Data System (ADS)

Veselkov, Alexei N.; Evstigneev, Maxim P.; Veselkov, Dennis A.; Davies, David B.

2001-08-01

A general nuclear magnetic resonance analysis of a statistical-thermodynamical model of hetero-association of aromatic molecules in solution has been developed to take "edge effects" into consideration, i.e., the dependence of proton chemical shifts on the position of the molecule situated inside or at the edge of the aggregate. This generalized approach is compared with a previously published model, where an average contribution to proton shielding is considered irrespective of the position of the molecule in the stack. Association parameters have been determined from experimental concentration and temperature dependences of 500 MHz proton chemical shifts of the hetero-association of the acridine dye, proflavine, and the phenanthridinium dye, ethidium bromide, in aqueous solution. Differences in the parameters in the range 10%-30% calculated using the basic and generalized approaches have been found to depend substantially on the magnitude of the equilibrium hetero-association constant Khet—the larger the value of Khet, the higher the discrepancy between the two methods.

Binding mechanism of PicoGreen to DNA characterized by magnetic tweezers and fluorescence spectroscopy.

PubMed

Wang, Ying; Schellenberg, Helene; Walhorn, Volker; Toensing, Katja; Anselmetti, Dario

2017-09-01

Fluorescent dyes are broadly used in many biotechnological applications to detect and visualize DNA molecules. However, their binding to DNA alters the structural and nanomechanical properties of DNA and, thus, interferes with associated biological processes. In this work we employed magnetic tweezers and fluorescence spectroscopy to investigate the binding of PicoGreen to DNA at room temperature in a concentration-dependent manner. PicoGreen is an ultrasensitive quinolinium nucleic acid stain exhibiting hardly any background signal from unbound dye molecules. By means of stretching and overwinding single, torsionally constrained, nick-free double-stranded DNA molecules, we acquired force-extension and supercoiling curves which allow quantifying DNA contour length, persistence length and other thermodynamical binding parameters, respectively. The results of our magnetic tweezers single-molecule binding study were well supported through analyzing the fluorescent spectra of stained DNA. On the basis of our work, we could identify a concentration-dependent bimodal binding behavior, where, apparently, PicoGreen associates to DNA as an intercalator and minor-groove binder simultaneously.

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.

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.

Iodinated Al(III)-based phthalocyanines are promising sensitizers for dye-sensitized solar cells; a theoretical comparison between Zn(II), Mg(II), and Al(III)-based phthalocyanine sensitizers.

PubMed

Yang, Li-Na; Sun, Zhu-Zhu; Chen, Shi-Lu; Li, Ze-Sheng

2014-02-24

To design efficient dyes for dye-sensitized solar cells (DSSCs), using a Zn-coordinated phthalocyanine (TT7) as the prototype, a series of phthalocyanine dyes (Pcs) with different metal ions and peripheral/axial groups have been investigated by means of density functional theory (DFT) and time-dependent DFT (TDDFT) methods. Computational results show that the iodinated Al-based dye with a peripheral amino group (Al-I-NH2-Pc) exhibits the largest redshift in the maximum absorbance (λ(max)). In addition, Al-based dyes have appropriate energy-level arrangements of frontier orbitals to keep excellent balance between electron injection and regeneration of oxidized dyes. Further, it has been found that the intermolecular π-staking interaction in Al-I-Pc molecules is weaker than the other metal-based Pcs, which may effectively reduce dye aggregation on the semi-conductor surface. All these results suggest iodinated Al-based Pcs (Al-I-Pcs) to be potentially promising sensitizers in DSSCs. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Adsorption of a cationic dye molecule on polystyrene microspheres in colloids: effect of surface charge and composition probed by second harmonic generation.

PubMed

Eckenrode, Heather M; Jen, Shih-Hui; Han, Jun; Yeh, An-Gong; Dai, Hai-Lung

2005-03-17

Nonlinear optical probe, second harmonic generation (SHG), of the adsorption of the dye molecule malachite green (MG), in cationic form at pH < or = 5, on polystyrene microspheres in aqueous solution is used to study the effect of surface charge and composition on molecular adsorption. Three types of polystyrene microspheres with different surface composition are investigated: (1) a sulfate terminated, anionic surface, (2) a neutral surface without any functional group termination, and (3) an amine terminated, cationic surface. The cationic dye was found to adsorb at all three surfaces, regardless of surface charge. The adsorption free energies, DeltaG's, measured for the three surfaces are -12.67, -12.39, and -10.46 kcal/mol, respectively, with the trend as expected from the charge interactions. The adsorption density on the anionic surface, where attractive charge-charge interaction dominates, is determined by the surface negative charge density. The adsorption densities on the neutral and cationic surfaces are on the other hand higher, perhaps as a result of a balance between minimizing repulsive charge interaction and maximizing attractive molecule-substrate and intermolecular interactions. The relative strength of the SH intensity per molecule, in combination of a model calculation, reveals that the C(2) axis of the MG molecule is nearly perpendicular to the surface on the anionic surface and tilts away from the surface norm when the surface is neutral and further away when cationic. Changing the pH of the solution may alter the surface charge and subsequently affect the adsorption configuration and SH intensity.

Orientation-Controllable ZnO Nanorod Array Using Imprinting Method for Maximum Light Utilization in Dye-Sensitized Solar Cells.

PubMed

Jeong, Huisu; Song, Hui; Lee, Ryeri; Pak, Yusin; Kumaresan, Yogeenth; Lee, Heon; Jung, Gun Young

2015-12-01

We present a holey titanium dioxide (TiO2) film combined with a periodically aligned ZnO nanorod layer (ZNL) for maximum light utilization in dye-sensitized solar cells (DSCs). Both the holey TiO2 film and the ZNL were simultaneously fabricated by imprint technique with a mold having vertically aligned ZnO nanorod (NR) array, which was transferred to the TiO2 film after imprinting. The orientation of the transferred ZNL such as laid, tilted, and standing ZnO NRs was dependent on the pitch and height of the ZnO NRs of the mold. The photoanode composed of the holey TiO2 film with the ZNL synergistically utilized the sunlight due to enhanced light scattering and absorption. The best power conversion efficiency of 8.5 % was achieved from the DSC with the standing ZNL, which represented a 33 % improvement compared to the reference cell with a planar TiO2.

Vertically aligned single-walled carbon nanotubes as low-cost and high electrocatalytic counter electrode for dye-sensitized solar cells.

PubMed

Dong, Pei; Pint, Cary L; Hainey, Mel; Mirri, Francesca; Zhan, Yongjie; Zhang, Jing; Pasquali, Matteo; Hauge, Robert H; Verduzco, Rafael; Jiang, Mian; Lin, Hong; Lou, Jun

2011-08-01

A novel dye-sensitized solar cell (DSSC) structure using vertically aligned single-walled carbon nanotubes (VASWCNTs) as the counter electrode has been developed. In this design, the VASWCNTs serve as a stable high surface area and highly active electrocatalytic counter-electrode that could be a promising alternative to the conventional Pt analogue. Utilizing a scalable dry transfer approach to form a VASWCNTs conductive electrode, the DSSCs with various lengths of VASWCNTs were studied. VASWCNTs-DSSC with 34 μm original length was found to be the optimal choice in the present study. The highest conversion efficiencies of VASWCNTs-DSSC achieved 5.5%, which rivals that of the reference Pt DSSC. From the electrochemical impedance spectroscopy analysis, it shows that the new DSSC offers lower interface resistance between the electrolyte and the counter electrode. This reproducible work emphasizes the promise of VASWCNTs as efficient and stable counter electrode materials in DSSC device design, especially taking into account the low-cost merit of this promising material.

Dye-controlled interfacial electron transfer for high-current indium tin oxide photocathodes.

PubMed

Huang, Zhongjie; He, Mingfu; Yu, Mingzhe; Click, Kevin; Beauchamp, Damian; Wu, Yiying

2015-06-01

Efficient sensitized photocathodes are highly desired for solar fuels and tandem solar cells, yet the development is hindered by the scarcity of suitable p-type semiconductors. The generation of high cathodic photocurrents by sensitizing a degenerate n-type semiconductor (tin-doped indium oxide; ITO) is reported. The sensitized mesoporous ITO electrodes deliver cathodic photocurrents of up to 5.96±0.19 mA cm(-2), which are close to the highest record in conventional p-type sensitized photocathodes. This is realized by the rational selection of dyes with appropriate energy alignments with ITO. The energy level alignment between the highest occupied molecular orbital of the sensitizer and the conduction band of ITO is crucial for efficient hole injection. Transient absorption spectroscopy studies demonstrate that the cathodic photocurrent results from reduction of the photoexcited sensitizer by free electrons in ITO. Our results reveal a new perspective toward the selection of electrode materials for sensitized photocathodes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redefining Molecular Amphipathicity in Reversing the "Coffee-Ring Effect": Implications for Single Base Mutation Detection.

PubMed

Huang, Chi; Wang, Jie; Lv, Xiaobo; Liu, Liu; Liang, Ling; Hu, Wei; Luo, Changliang; Wang, Fubing; Yuan, Quan

2018-05-21

The "coffee ring effect" is a natural phenomenon where sessile drops leave ring-shaped structures on solid surfaces upon drying. It drives non-uniform deposition of suspended compounds on substrates, which adversely affects many processes, including surface-assisted biosensing and molecular self-assembly. In this study, we describe how the coffee ring effect can be eliminated by controlling the amphipathicity of the suspended compounds, for example DNA modified with hydrophobic dye. Specifically, nuclease digestion of the hydrophilic DNA end converts the dye-labeled molecule into an amphipathic molecule (one with comparably weighted hydrophobic and hydrophilic ends) and reverses the coffee ring effect and results in uniform disc-shaped feature deposition of the dye. The amphipathic product decreases the surface tension of the sessile drops and induces Marangoni flow, which drives the uniform distribution of the amphipathic dye-labeled product in the drops. As proof-of-concept, this strategy was used in a novel enzymatic amplification method for biosensing to eliminate the coffee ring effect on a nitrocellulose membrane and increase assay reliability and sensitivity. Importantly, the reported strategy for eliminating the coffee ring effect can be extended to other sessile drop systems for potentially improving assay reliability, and sensitivity.

Diffractive imaging of a rotational wavepacket in nitrogen molecules with femtosecond megaelectronvolt electron pulses

DOE PAGES

Yang, Jie; Guehr, Markus; Vecchione, Theodore; ...

2016-04-05

Imaging changes in molecular geometries on their natural femtosecond timescale with sub-Angström spatial precision is one of the critical challenges in the chemical sciences, as the nuclear geometry changes determine the molecular reactivity. For photoexcited molecules, the nuclear dynamics determine the photoenergy conversion path and efficiency. Here we report a gas-phase electron diffraction experiment using megaelectronvolt (MeV) electrons, where we captured the rotational wavepacket dynamics of nonadiabatically laser-aligned nitrogen molecules. We achieved a combination of 100 fs root-mean-squared temporal resolution and sub-Angstrom (0.76 Å) spatial resolution that makes it possible to resolve the position of the nuclei within the molecule.more » In addition, the diffraction patterns reveal the angular distribution of the molecules, which changes from prolate (aligned) to oblate (anti-aligned) in 300 fs. Lastly, our results demonstrate a significant and promising step towards making atomically resolved movies of molecular reactions.« less

Versatile alignment layer method for new types of liquid crystal photonic devices

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

Finnemeyer, V.; Bryant, D.; Lu, L.

2015-07-21

Liquid crystal photonic devices are becoming increasingly popular. These devices often present a challenge when it comes to creating a robust alignment layer in pre-assembled cells. In this paper, we describe a method of infusing a dye into a microcavity to produce an effective photo-definable alignment layer. However, previous research on such alignment layers has shown that they have limited stability, particularly against subsequent light exposure. As such, we further describe a method of utilizing a pre-polymer, infused into the microcavity along with the liquid crystal, to provide photostability. We demonstrate that the polymer layer, formed under ultraviolet irradiation ofmore » liquid crystal cells, has been effectively localized to a thin region near the substrate surface and provides a significant improvement in the photostability of the liquid crystal alignment. This versatile alignment layer method, capable of being utilized in devices from the described microcavities to displays, offers significant promise for new photonics applications.« less

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

Discovery of black dye crystal structure polymorphs: Implications for dye conformational variation in dye-sensitized solar cells

DOE PAGES

Cole, Jacqueline M.; Low, Kian Sing; Gong, Yun

2015-11-24

Here, we present the discovery of a new crystal structure polymorph (1) and pseudopolymorph (2) of the Black Dye, one of the world’s leading dyes for dye-sensitized solar cells, DSSCs (10.4% device performance efficiency). This reveals that Black Dye molecules can adopt multiple low-energy conformers. This is significant since it challenges existing models of the Black Dye···TiO 2 adsorption process that renders a DSSC working electrode; these have assumed a single molecular conformation that refers to the previously reported Black Dye crystal structure (3). The marked structural differences observed between 1, 2, and 3 make the need for modeling multiplemore » conformations more acute. Additionally, the ordered form of the Black Dye (1) provides a more appropriate depiction of its anionic structure, especially regarding its anchoring group and NCS bonding descriptions. The tendency toward NCS ligand isomerism, evidenced via the disordered form 2, has consequences for electron injection and electron recombination in Black Dye embedded DSSC devices. Dyes 2 and 3 differ primarily by the absence or presence of a solvent of crystallization, respectively; solvent environment effects on the dye are thereby elucidated. This discovery of multiple Black Dye conformers from diffraction, with atomic-level definition, complements recently reported nanoscopic evidence for multiple dye conformations existing at a dye···TiO 2 interface, for a chemically similar DSSC dye; those results emanated from imaging and spectroscopy, but were unresolved at the submolecular level. Taken together, these findings lead to the general notion that multiple dye conformations should be explicitly considered when modeling dye···TiO 2 interfaces in DSSCs, at least for ruthenium-based dye complexes.« less

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.

Nanodevices for generating power from molecules and batteryless sensing

DOEpatents

Wang, Yinmin; Wang, Xianying; Hamza, Alex V.

2017-01-03

A nanoconverter or nanosensor is disclosed capable of directly generating electricity through physisorption interactions with molecules that are dipole containing organic species in a molecule interaction zone. High surface-to-volume ratio semiconductor nanowires or nanotubes (such as ZnO, silicon, carbon, etc.) are grown either aligned or randomly-aligned on a substrate. Epoxy or other nonconductive polymers are used to seal portions of the nanowires or nanotubes to create molecule noninteraction zones. By correlating certain molecule species to voltages generated, a nanosensor may quickly identify which species is detected. Nanoconverters in a series parallel arrangement may be constructed in planar, stacked, or rolled arrays to supply power to nano- and micro-devices without use of external batteries. In some cases breath, from human or other life forms, contain sufficient molecules to power a nanoconverter. A membrane permeable to certain molecules around the molecule interaction zone increases specific molecule nanosensor selectivity response.

Nanodevices for generating power from molecules and batteryless sensing

DOEpatents

Wang, Yinmin; Wang, Xianying; Hamza, Alex V.

2015-06-09

A nanoconverter or nanosensor is disclosed capable of directly generating electricity through physisorption interactions with molecules that are dipole containing organic species in a molecule interaction zone. High surface-to-volume ratio semiconductor nanowires or nanotubes (such as ZnO, silicon, carbon, etc.) are grown either aligned or randomly-aligned on a substrate. Epoxy or other nonconductive polymers are used to seal portions of the nanowires or nanotubes to create molecule noninteraction zones. By correlating certain molecule species to voltages generated, a nanosensor may quickly identify which species is detected. Nanoconverters in a series parallel arrangement may be constructed in planar, stacked, or rolled arrays to supply power to nano- and micro-devices without use of external batteries. In some cases breath, from human or other life forms, contain sufficient molecules to power a nanoconverter. A membrane permeable to certain molecules around the molecule interaction zone increases specific molecule nanosensor selectivity response.

Nanodevices for generating power from molecules and batteryless sensing

DOEpatents

Wang, Yinmin; Wang, Xianying; Hamza, Alex V.

2014-07-15

A nanoconverter or nanosensor is disclosed capable of directly generating electricity through physisorption interactions with molecules that are dipole containing organic species in a molecule interaction zone. High surface-to-volume ratio semiconductor nanowires or nanotubes (such as ZnO, silicon, carbon, etc.) are grown either aligned or randomly-aligned on a substrate. Epoxy or other nonconductive polymers are used to seal portions of the nanowires or nanotubes to create molecule noninteraction zones. By correlating certain molecule species to voltages generated, a nanosensor may quickly identify which species is detected. Nanoconverters in a series parallel arrangement may be constructed in planar, stacked, or rolled arrays to supply power to nano- and micro-devices without use of external batteries. In some cases breath, from human or other life forms, contain sufficient molecules to power a nanoconverter. A membrane permeable to certain molecules around the molecule interaction zone increases specific molecule nanosensor selectivity response.

Motuporamine Derivatives as Antimicrobial Agents and Antibiotic Enhancers against Resistant Gram-Negative Bacteria.

PubMed

Borselli, Diane; Blanchet, Marine; Bolla, Jean-Michel; Muth, Aaron; Skruber, Kristen; Phanstiel, Otto; Brunel, Jean Michel

2017-02-01

Dihydromotuporamine C and its derivatives were evaluated for their in vitro antimicrobial activities and antibiotic enhancement properties against Gram-negative bacteria and clinical isolates. The mechanism of action of one of these derivatives, MOTU-N44, was investigated against Enterobacter aerogenes by using fluorescent dyes to evaluate outer-membrane depolarization and permeabilization. Its efficiency correlated with inhibition of dye transport, thus suggesting that these molecules inhibit drug transporters by de-energization of the efflux pump rather than by direct interaction of the molecule with the pump. This suggests that depowering the efflux pump provides another strategy to address antibiotic resistance. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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

Giant Raman scattering from J-aggregated dyes inside carbon nanotubes for multispectral imaging

NASA Astrophysics Data System (ADS)

Gaufrès, E.; Tang, N. Y.-Wa; Lapointe, F.; Cabana, J.; Nadon, M.-A.; Cottenye, N.; Raymond, F.; Szkopek, T.; Martel, R.

2014-01-01

Raman spectroscopy uses visible light to acquire vibrational fingerprints of molecules, thus making it a powerful tool for chemical analysis in a wide range of media. However, its potential for optical imaging at high resolution is severely limited by the fact that the Raman effect is weak. Here, we report the discovery of a giant Raman scattering effect from encapsulated and aggregated dye molecules inside single-walled carbon nanotubes. Measurements performed on rod-like dyes such as α-sexithiophene and β-carotene, assembled inside single-walled carbon nanotubes as highly polarizable J-aggregates, indicate a resonant Raman cross-section of (3 +/- 2) × 10-21 cm2 sr-1, which is well above the cross-section required for detecting individual aggregates at the highest optical resolution. Free from fluorescence background and photobleaching, this giant Raman effect allows the realization of a library of functionalized nanoprobe labels for Raman imaging with robust detection using multispectral analysis.

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.

Enzymatic production of single-molecule FISH and RNA capture probes.

PubMed

Gaspar, Imre; Wippich, Frank; Ephrussi, Anne

2017-10-01

Arrays of singly labeled short oligonucleotides that hybridize to a specific target revolutionized RNA biology, enabling quantitative, single-molecule microscopy analysis and high-efficiency RNA/RNP capture. Here, we describe a simple and efficient method that allows flexible functionalization of inexpensive DNA oligonucleotides by different fluorescent dyes or biotin using terminal deoxynucleotidyl transferase and custom-made functional group conjugated dideoxy-UTP. We show that (i) all steps of the oligonucleotide labeling-including conjugation, enzymatic synthesis, and product purification-can be performed in a standard biology laboratory, (ii) the process yields >90%, often >95% labeled product with minimal carryover of impurities, and (iii) the oligonucleotides can be labeled with different dyes or biotin, allowing single-molecule FISH, RNA affinity purification, and Northern blot analysis to be performed. © 2017 Gaspar et al.; Published by Cold Spring Harbor Laboratory Press for the RNA Society.

LIMAO: Cross-platform software for simulating laser-induced alignment and orientation dynamics of linear-, symmetric- and asymmetric tops

NASA Astrophysics Data System (ADS)

Szidarovszky, Tamás; Jono, Maho; Yamanouchi, Kaoru

2018-07-01

A user-friendly and cross-platform software called Laser-Induced Molecular Alignment and Orientation simulator (LIMAO) has been developed. The program can be used to simulate within the rigid rotor approximation the rotational dynamics of gas phase molecules induced by linearly polarized intense laser fields at a given temperature. The software is implemented in the Java and Mathematica programming languages. The primary aim of LIMAO is to aid experimental scientists in predicting and analyzing experimental data representing laser-induced spatial alignment and orientation of molecules.

Capillary array scanner for time-resolved detection and identification of fluorescently labelled DNA fragments.

PubMed

Neumann, M; Herten, D P; Dietrich, A; Wolfrum, J; Sauer, M

2000-02-25

The first capillary array scanner for time-resolved fluorescence detection in parallel capillary electrophoresis based on semiconductor technology is described. The system consists essentially of a confocal fluorescence microscope and a x,y-microscope scanning stage. Fluorescence of the labelled probe molecules was excited using a short-pulse diode laser emitting at 640 nm with a repetition rate of 50 MHz. Using a single filter system the fluorescence decays of different labels were detected by an avalanche photodiode in combination with a PC plug-in card for time-correlated single-photon counting (TCSPC). The time-resolved fluorescence signals were analyzed and identified by a maximum likelihood estimator (MLE). The x,y-microscope scanning stage allows for discontinuous, bidirectional scanning of up to 16 capillaries in an array, resulting in longer fluorescence collection times per capillary compared to scanners working in a continuous mode. Synchronization of the alignment and measurement process were developed to allow for data acquisition without overhead. Detection limits in the subzeptomol range for different dye molecules separated in parallel capillaries have been achieved. In addition, we report on parallel time-resolved detection and separation of more than 400 bases of single base extension DNA fragments in capillary array electrophoresis. Using only semiconductor technology the presented technique represents a low-cost alternative for high throughput DNA sequencing in parallel capillaries.

Optical control of ground-state atomic orbital alignment: Cl(2P3/2) atoms from HCl(v=2,J=1) photodissociation.

PubMed

Sofikitis, Dimitris; Rubio-Lago, Luis; Martin, Marion R; Ankeny Brown, Davida J; Bartlett, Nathaniel C-M; Alexander, Andrew J; Zare, Richard N; Rakitzis, T Peter

2007-10-14

H(35)Cl(v=0,J=0) molecules in a supersonic expansion were excited to the H(35)Cl(v=2,J=1,M=0) state with linearly polarized laser pulses at about 1.7 microm. These rotationally aligned J=1 molecules were then selectively photodissociated with a linearly polarized laser pulse at 220 nm after a time delay, and the velocity-dependent alignment of the (35)Cl((2)P(32)) photofragments was measured using 2+1 REMPI and time-of-flight mass spectrometry. The (35)Cl((2)P(32)) atoms are aligned by two mechanisms: (1) the time-dependent transfer of rotational polarization of the H(35)Cl(v=2,J=1,M=0) molecule to the (35)Cl((2)P(32)) nuclear spin [which is conserved during the photodissociation and thus contributes to the total (35)Cl((2)P(32)) photofragment atomic polarization] and (2) the alignment of the (35)Cl((2)P(32)) electronic polarization resulting from the photoexcitation and dissociation process. The total alignment of the (35)Cl((2)P(32)) photofragments from these two mechanisms was found to vary as a function of time delay between the excitation and the photolysis laser pulses, in agreement with theoretical predictions. We show that the alignment of the ground-state (35)Cl((2)P(32)) atoms, with respect to the photodissociation recoil direction, can be controlled optically. Potential applications include the study of alignment-dependent collision effects.

A practical strategy for the accurate measurement of residual dipolar couplings in strongly aligned small molecules

NASA Astrophysics Data System (ADS)

Liu, Yizhou; Cohen, Ryan D.; Martin, Gary E.; Williamson, R. Thomas

2018-06-01

Accurate measurement of residual dipolar couplings (RDCs) requires an appropriate degree of alignment in order to optimize data quality. An overly weak alignment yields very small anisotropic data that are susceptible to measurement errors, whereas an overly strong alignment introduces extensive anisotropic effects that severely degrade spectral quality. The ideal alignment amplitude also depends on the specific pulse sequence used for the coupling measurement. In this work, we introduce a practical strategy for the accurate measurement of one-bond 13C-1H RDCs up to a range of ca. -300 to +300 Hz, corresponding to an alignment that is an order of magnitude stronger than typically employed for small molecule structural elucidation. This strong alignment was generated in the mesophase of the commercially available poly-γ-(benzyl-L-glutamate) polymer. The total coupling was measured by the simple and well-studied heteronuclear two-dimensional J-resolved experiment, which performs well in the presence of strong anisotropic effects. In order to unequivocally determine the sign of the total coupling and resolve ambiguities in assigning total couplings in the CH2 group, coupling measurements were conducted at an isotropic condition plus two anisotropic conditions of different alignment amplitudes. Most RDCs could be readily extracted from these measurements whereas more complicated spectral effects resulting from strong homonuclear coupling could be interpreted either theoretically or by simulation. Importantly, measurement of these very large RDCs actually offers significantly improved data quality and utility for the structure determination of small organic molecules.

Stability and efficiency of dye-sensitized solar cells based on papaya-leaf dye.

PubMed

Suyitno, Suyitno; Saputra, Trisma Jaya; Supriyanto, Agus; Arifin, Zainal

2015-09-05

The present article reports on the enhancement of the performance and stability of natural dye-based dye-sensitized solar cells (DSSCs). Natural dyes extracted from papaya leaves (PL) were investigated as sensitizers in TiO2-based DSSCs and evaluated in comparison with N719 dye. The acidity of the papaya-leaf extract dyes was tuned by adding benzoic acid. The TiO2 film-coated fluorine-doped tin oxide glass substrates were prepared using the doctor-blade method, followed by sintering at 450 °C. The counter electrode was coated by chemically deposited catalytic platinum. The working electrodes were immersed in N719 dye and papaya dye solutions with concentrations of 8 g/100 mL. The absorbance spectra of the dyes were obtained by ultra-violet-visible spectroscopy. The energy levels of the dyes were measured by the method of cyclic voltammetry. In addition, Fourier transform infrared spectroscopy was used to determine the characteristic functionalities of the dye molecules. The DSSC based on the N719 dye displayed a highest efficiency of 0.87% whereas those based on papaya-leaf dye achieved 0.28% at pH 3.5. The observed improved efficiency of the latter was attributed to the increased current density value. Furthermore, the DSSCs based on papaya-leaf dye with pH 3.5-4 exhibited better stability than those based on N719 dye. However, further studies are required to improve the current density and stability of natural dye-based DSSCs, including the investigation of alternative dye extraction routes, such as isolating the pure chlorophyll from papaya leaves and stabilizing it. Copyright © 2015 Elsevier B.V. All rights reserved.

Stability and efficiency of dye-sensitized solar cells based on papaya-leaf dye

NASA Astrophysics Data System (ADS)

Suyitno, Suyitno; Saputra, Trisma Jaya; Supriyanto, Agus; Arifin, Zainal

2015-09-01

The present article reports on the enhancement of the performance and stability of natural dye-based dye-sensitized solar cells (DSSCs). Natural dyes extracted from papaya leaves (PL) were investigated as sensitizers in TiO2-based DSSCs and evaluated in comparison with N719 dye. The acidity of the papaya-leaf extract dyes was tuned by adding benzoic acid. The TiO2 film-coated fluorine-doped tin oxide glass substrates were prepared using the doctor-blade method, followed by sintering at 450 °C. The counter electrode was coated by chemically deposited catalytic platinum. The working electrodes were immersed in N719 dye and papaya dye solutions with concentrations of 8 g/100 mL. The absorbance spectra of the dyes were obtained by ultra-violet-visible spectroscopy. The energy levels of the dyes were measured by the method of cyclic voltammetry. In addition, Fourier transform infrared spectroscopy was used to determine the characteristic functionalities of the dye molecules. The DSSC based on the N719 dye displayed a highest efficiency of 0.87% whereas those based on papaya-leaf dye achieved 0.28% at pH 3.5. The observed improved efficiency of the latter was attributed to the increased current density value. Furthermore, the DSSCs based on papaya-leaf dye with pH 3.5-4 exhibited better stability than those based on N719 dye. However, further studies are required to improve the current density and stability of natural dye-based DSSCs, including the investigation of alternative dye extraction routes, such as isolating the pure chlorophyll from papaya leaves and stabilizing it.

Control of Resonances and Optical Properties of Plasmonic-Patch Metamaterials

DTIC Science & Technology

2012-08-01

entitled "Control of resonances and optical properties of plasmonic-patch metamaterials", under Award No. FA2386-11-1-4707 The stated research goals...their photonic properties when nonlinear amplifying dye molecules are imbedded in the structures. We will particularly focus on three...metamaterial structures. 4. Measurement of plasmon resonance and florescence properties in the dye-doped metamaterials with and without the

Thermally controlled preferential molecular aggregation state in a thiacarbocyanine dye

NASA Astrophysics Data System (ADS)

Passier, Rémy; Ritchie, James P.; Toro, Carlos; Diaz, Carlos; Masunov, Artëm E.; Belfield, Kevin D.; Hernandez, Florencio E.

2010-10-01

Herein we report the experimental and theoretical study of the temperature dependence of a thiacarbocyanine dye in its monomer, H- and J-aggregates states. We demonstrate the ability to control the ratio of monomer, H- and/or J-aggregates with heat. We link such a control to the conformation dependence of the molecule. An alternative way to gain access to the dominating species without changing the concentration as a complete switching mechanism between all the present species is proposed. The results presented in this work lead to a better understanding of thiacarbocyanine dye's behavior.

Design considerations for multi component molecular-polymeric nonlinear optical materials

NASA Astrophysics Data System (ADS)

Singer, K. D.; Kuzyk, M. G.; Fang, T.; Holland, W. R.; Cahill, P. A.

1990-08-01

We review our work on multi component polymeric nonlinear optical materials. These materials consist of nonlinear optical molecules incorporated in a polymeric host. A cross-linked triazine polymer incorporating a dicyanovinyl terminated azo dye was found to be relatively stable at 85 deg and possess an electro-optic coefficient of 11pm/V. We have also observed the zero dispersion condition in a new anomalous dispersion dye for phase matched second harmonic generation, and expect efficient conversion to the blue. A squarylium dye, ISQ, has been found to possess a large third order nonlinearity, and may display two-level behavior.

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.

From nanocorals to nanorods to nanoflowers nanoarchitecture for efficient dye-sensitized solar cells at relatively low film thickness: All Hydrothermal Process

NASA Astrophysics Data System (ADS)

Mali, Sawanta S.; Betty, Chirayath A.; Bhosale, Popatrao N.; Patil, Pramod S.; Hong, Chang Kook

2014-06-01

Simple and low temperature hydrothermal process is employed to synthesize exotic nanostructures of TiO2. The nanostructures are obtained merely by changing the nature of the precursors and processing parameters. The chloride and isopropoxide salts of titanium are used to grow high quality thin films comprising anatase nanocorals, rutile nanorods and rutile nanoflowers respectively. A novel route of addition of room temperature ionic liquid (RTIL) is used to synthesize hitherto unexplored nano-morphologies. The Bronsted Acidic Ionic Liquid [BAIL] 0.01 M, 1: 3-ethoxycarbonylethyl-1-methyl-imidazolium chloride [CMIM][HSO4] RTIL directed growth of TiO2 flowers with bunch of aligned nanorods are obtained. The structural, optical and morphological properties of hydrothermally grown TiO2 samples are studied with the different characterization techniques. The influence of these exotic nano-morphologies on the performance of dye sensitized solar cells (DSSCs) is investigated in detail. It is found that [CMIM][HSO4] can facilitate the formation of novel nanoflower morphology with uniform, dense, and collectively aligned in regular petal like oriented TiO2 nanorods and hence improves the dye adsorption and the photovoltaic performance of DSSCs, typically in short-circuit photocurrent and power conversion efficiency. A best power conversion efficiency of 6.63% has been achieved on a DSSC based on nanoflowers (TNF) film obtained from a [CMIM][HSO4] solution.

Effects of diode laser welding with dye-enhanced glue on tensile strength of sutures commonly used in urology.

PubMed

Kirsch, A J; Chang, D T; Kayton, M L; Libutti, S K; Connor, J P; Hensle, T W

1996-01-01

Tissue welding using laser-activated protein solders may soon become an alternative to sutured tissue approximation. In most cases, approximating sutures are used both to align tissue edges and provide added tensile strength. Collateral thermal injury, however, may cause disruption of tissue alignment and weaken the tensile strength of sutures. The objective of this study was to evaluate the effect of laser welding on the tensile strength of suture materials used in urologic surgery. Eleven types of sutures were exposed to diode laser energy (power density = 15.9 W/cm2) for 10, 30, and 60 seconds. Each suture was compared with and without the addition of dye-enhanced albumin-based solder. After exposure, each suture material was strained (2"/min) until ultimate breakage on a tensometer and compared to untreated sutures using ANOVA. The strength of undyed sutures were not significantly affected; however, violet and green-dyed sutures were in general weakened by laser exposure in the presence of dye-enhanced glue. Laser activation of the smallest caliber, dyed sutures (7-0) in the presence of glue caused the most significant loss of tensile strength of all sutures tested. These results indicate that the thermal effects of laser welding using our technique decrease the tensile strength of dyed sutures. A thermally resistant suture material (undyed or clear) may prevent disruption of wounds closed by laser welding techniques.

Density functional theory study of adsorption geometries and electronic structures of azo-dye-based molecules on anatase TiO2 surface for dye-sensitized solar cell applications.

PubMed

Prajongtat, Pongthep; Suramitr, Songwut; Nokbin, Somkiat; Nakajima, Koichi; Mitsuke, Koichiro; Hannongbua, Supa

2017-09-01

Structural and electronic properties of eight isolated azo dyes (ArNNAr', where Ar and Ar' denote the aryl groups containing benzene and naphthalene skeletons, respectively) were investigated by density functional theory (DFT) based on the B3LYP/6-31G(d,p) and TD-B3LYP/6-311G(d,p) methods The effect of methanol solvent on the structural and electronic properties of the azo dyes was elucidated by employing a polarizable continuum model (PCM). Then, the azo dyes adsorbed onto the anatase TiO 2 (101) slab surface through a carboxyl group. The geometries and electronic structures of the adsorption complexes were determined using periodic DFT based on the PWC/DNP method. The calculated adsorption energies indicate that the adsorbed dyes preferentially take configuration of the bidentate bridging rather than chelating or monodentate ester-type geometries. Furthermore, the azo compounds having two carboxyl groups are coordinated to the TiO 2 surface more preferentially through the carboxyl group connecting to the benzene skeleton than through that connecting to the naphthalene skeleton. The dihedral angles (Φ B-N ) between the benzene- and naphthalene-skeleton moieties are smaller than 10° for the adsorbed azo compounds containing one carboxyl group. In contrast, Φ B-N > 30° are obtained for the adsorbed azo compounds containing two carboxyl groups. The almost planar conformations of the former appear to strengthen both π-electrons conjugation and electronic coupling between low-lying unoccupied molecular orbitals of the azo dyes and the conduction band of TiO 2 . On the other hand, such coupling is very weak for the latter, leading to a shift of the Fermi level of TiO 2 in the lower-energy direction. The obtained results are useful to the design and synthesize novel azo-dye-based molecules that give rise to higher photovoltaic performances of the dye-sensitized solar cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Digital DNA detection based on a compact optofluidic laser with ultra-low sample consumption.

PubMed

Lee, Wonsuk; Chen, Qiushu; Fan, Xudong; Yoon, Dong Ki

2016-11-29

DNA lasers self-amplify optical signals from a DNA analyte as well as thermodynamic differences between sequences, allowing quasi-digital DNA detection. However, these systems have drawbacks, such as relatively large sample consumption and complicated dye labelling. Moreover, although the lasing signal can detect the target DNA, it is superimposed on an unintended fluorescence background, which persists for non-target DNA samples as well. From an optical point of view, it is thus not truly digital detection and requires spectral analysis to identify the target. In this work, we propose and demonstrate an optofluidic laser that has a single layer of DNA molecules as the gain material. A target DNA produces intensive laser emission comparable to existing DNA lasers, while any unnecessary fluorescence background is successfully suppressed. As a result, the target DNA can be detected with a single laser pulse, in a truly digital manner. Since the DNA molecules cover only a single layer on the surface of the laser microcavity, the DNA sample consumption is a few orders of magnitude lower than that of existing DNA lasers. Furthermore, the DNA molecules are stained by simply immersing the microcavity in the intercalating dye solution, and thus the proposed DNA laser is free of any complex dye-labelling process prior to analysis.

Homogeneous assay of target molecules based on chemiluminescence resonance energy transfer (CRET) using DNAzyme-linked aptamers.

PubMed

Mun, Hyoyoung; Jo, Eun-Jung; Li, Taihua; Joung, Hyou-Arm; Hong, Dong-Gu; Shim, Won-Bo; Jung, Cheulhee; Kim, Min-Gon

2014-08-15

We have designed a single-stranded DNAzyme-aptamer sensor for homogeneous target molecular detection based on chemiluminescence resonance energy transfer (CRET). The structure of the engineered single-stranded DNA (ssDNA) includes the horseradish peroxidase (HRP)-like DNAzyme, optimum-length linker (10-mer-length DNA), and target-specific aptamer sequences. A quencher dye was modified at the 3' end of the aptamer sequence. The incorporation of hemin into the G-quadruplex structure of DNAzyme yields an active HRP-like activity that catalyzes luminol to generate a chemiluminescence (CL) signal. In the presence of target molecules, such as ochratoxin A (OTA), adenosine triphosphate (ATP), or thrombin, the aptamer sequence was folded due to the formation of the aptamer/analyte complex, which induced the quencher dye close to the DNAzyme structure. Consequently, the CRET occurred between a DNAzyme-catalyzed chemiluminescence reaction and the quencher dye. Our results showed that CRET-based DNAzyme-aptamer biosensing enabled specific OTA analysis with a limit of detection of 0.27ng/mL. The CRET platform needs no external light source and avoids autofluorescence and photobleaching, and target molecules can be detected specifically and sensitively in a homogeneous manner. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Conformation of nanoconfined DNA as a function of ATP, AMP, CTP, Mg2+, and dye binding

NASA Astrophysics Data System (ADS)

Roushan, Maedeh; Riehn, Robert

2014-03-01

DNA molecules stretch in nanochannels with a channel cross-section of 100x100 nm2, thereby allowing analysis by observation of a fluorescent dye. The length and configuration of DNA can be directly observed, and the effect of different DNA-binding proteins on DNA configuration can be studied. Recently, we reported on the ability of T4 ligase to transiently manipulate DNA as a function of ATP and magnesium exposure. In this process we have extensively probed the interactions of dyes and enzyme co-factors with DNA under nanoconfinement. We find negligible effects if DNA is visualized using groove-binding dyes such as DAPI. However, if an intercalating dye (YOYO-1) is used, we find a significant shortening of the DNA in the presence of ATP that we attribute to an interaction of dye and ATP (as well as AMP and CTP). We did not record a noticeable effect due to Mg2+.

Surface activity of branched alkylamino-compounds and their influence on phase transfer behavior in water solutions of dyes

NASA Astrophysics Data System (ADS)

Li, Cuiqin; Guo, Suyue; Lin, Zhiyu; Wang, Jun; Ge, Tengjie

2016-02-01

Two branched alkylamino-compounds (AAC, R12-0.5G, and R12-1.0G), were synthesized from dodecylamine, methyl acrylate and ethylenediamine. The surface tension measurements on branched alkylamino- compounds demonstrated that surface activity of R12-1.0G is superior to that of R12-0.5G at 25°C. It has been found that the self-assembly of R12-1.0G and lauric acid formed by electrostatic interaction and the self-assembly of the molecule might transfer water-soluble dyes from water to toluene. These AAC might be applied for treating dyes in wastewater. The mass ratio of lauric to toluene, the concentration of R12-1.0G, and hydrophilic groups of dyes affected the transfer rate of the water-soluble dyes. The transfer rates of the watersoluble dyes by R12-1.0G were higher than that of 1.0G polyacrylamide-acrylamide.

Spectral-Polarization Properties and Light Resistance of Polyvinyl-Alcohol Films Colored With Disazo Dyes

NASA Astrophysics Data System (ADS)

Fillipovich, L. N.; Ariko, N. G.; Agabekov, V. E.; Malashko, P. M.

2005-09-01

Polarizers containing disazo dyes from the group of azobenzene-azonaphthalene have been developed. It has been established that their polarizing ability is determined by the mutual disposition of the azo group and electron-donor substituents in the naphthalene ring. On diazo coupling of γ acid into the α position relative to the oxy group, the M1 and M3 dyes are formed, the polarizing ability of which in uniaxially oriented polyvinyl-alcohol films is higher than in the M2 dye produced as a result of diazo coupling into the α position relative to the amino group. On irradiation by UV light, the dyes are subjected to photodestruction, which, in the case of M2, proceeds through trans-cis-isomerization. The rate of photodestruction depends on the aggregation of the dye molecules, and it increases in the presence of a free-radical initiator. The UV absorber (substituted benzotriazole) and the uniaxial orientation of the film retard this process.

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.

Dye removal from textile industrial effluents by adsorption on exfoliated graphite nanoplatelets: kinetic and equilibrium studies.

PubMed

Carvallho, Marilda N; da Silva, Karolyne S; Sales, Deivson C S; Freire, Eleonora M P L; Sobrinho, Maurício A M; Ghislandi, Marcos G

2016-01-01

The concept of physical adsorption was applied for the removal of direct and reactive blue textile dyes from industrial effluents. Commercial graphite nanoplatelets were used as substrate, and the quality of the material was characterized by atomic force and transmission electron microscopies. Dye/graphite nanoplatelets water solutions were prepared varying their pH and initial dye concentration. Exceptionally high values (beyond 100 mg/L) for adsorptive capacity of graphite nanoplatelets could be achieved without complicated chemical modifications, and equilibrium and kinetic experiments were performed. Our findings were compared with the state of the art, and compared with theoretical models. Agreement between them was satisfactory, and allowed us to propose novel considerations describing the interactions of the dyes and the graphene planar structure. The work highlights the important role of these interactions, which can govern the mobility of the dye molecules and the amount of layers that can be stacked on the graphite nanoplatelets surface.

One-step synthesis of vertically aligned anatase thornbush-like TiO2 nanowire arrays on transparent conducting oxides for solid-state dye-sensitized solar cells.

PubMed

Roh, Dong Kyu; Chi, Won Seok; Ahn, Sung Hoon; Jeon, Harim; Kim, Jong Hak

2013-08-01

Herein, we report a facile synthesis of high-density anatase-phase vertically aligned thornbush-like TiO2 nanowires (TBWs) on transparent conducting oxide glasses. Morphologically controllable TBW arrays of 9 μm in length are generated through a one-step hydrothermal reaction at 200 °C over 11 h using potassium titanium oxide oxalate dehydrate, diethylene glycol (DEG), and water. The TBWs consist of a large number of nanoplates or nanorods, as confirmed by SEM and TEM imaging. The morphologies of TBWs are controllable by adjusting DEG/water ratios. TBW diameters gradually decrease from 600 (TBW600) to 400 (TBW400) to 200 nm (TBW200) and morphologies change from nanoplates to nanorods with an increase in DEG content. TBWs are utilized as photoanodes for quasi-solid-state dye-sensitized solar cells (qssDSSCs) and solid-state DSSCs (ssDSSCs). The energy-conversion efficiency of qssDSSCs is in the order: TBW200 (5.2%)>TBW400 (4.5%)>TBW600 (3.4%). These results can be attributed to the different surface areas, light-scattering effects, and charge transport rates, as confirmed by dye-loading measurements, reflectance spectroscopy, and incident photon-to-electron conversion efficiency and intensity-modulated photovoltage spectroscopy/intensity-modulated photocurrent spectroscopy analyses. TBW200 is further treated with a graft-copolymer-directed organized mesoporous TiO2 to increase the surface area and interconnectivity of TBWs. As a result, the energy-conversion efficiency of the ssDSSC increases to 6.7% at 100 mW cm(-2) , which is among the highest values for N719-dye-based ssDSSCs. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Comparative Study on the Photophysics and Photochemistry of Xanthene Dyes in the Presence of Polyamidoamine (PAMAM) Dendrimers.

PubMed

Arbeloa, Ernesto Maximiliano; Previtali, Carlos Mario; Bertolotti, Sonia Graciela

2018-04-17

The photophysical and photochemical properties of the xanthene dyes Eosin Y, Erythrosin B, and Rose Bengal are evaluated in the presence of amino-terminated polyamidoamine (PAMAM) dendrimers of relatively high generation (G3-G5) in alkaline aqueous solution. UV/Vis absorption and fluorescence spectra of the dyes show bathochromic shifts, which correlate with the size of the dendrimer. Binding constants (K bind ) are calculated from absorption data. The resulting high K bind values indicate strong interactions between both molecules. Triplet-triplet absorption spectra of the dyes are recorded by laser flash photolysis, and a decrease in the triplet lifetimes is observed in the presence of dendrimers. At the same time, an increase in the absorption of the semireduced form of the dyes is observed. Rate constants for triplet quenching ( 3 k q ) and radical quantum yields (Φ R ) are obtained. The results are explained by a very efficient electron-transfer process from PAMAM to xanthene dyes for all of the dye/dendrimer couples that are evaluated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic reduction of organic dyes at gold nanoparticles impregnated silica materials: influence of functional groups and surfactants

NASA Astrophysics Data System (ADS)

Azad, Uday Pratap; Ganesan, Vellaichamy; Pal, Manas

2011-09-01

Gold nanoparticles (Au NPs) in three different silica based sol-gel matrixes with and without surfactants are prepared. They are characterized by UV-vis absorbance and transmission electron microscopic (TEM) studies. The size and shape of Au NPs varied with the organo-functional group present in the sol-gel matrix. In the presence of mercaptopropyl functionalized organo-silica, large sized (200-280 nm) spherical Au NPs are formed whereas in the presence of aminopropyl functionalized organo-silica small sized (5-15 nm) Au NPs are formed inside the tube like organo-silica. Further, it is found that Au NPs act as efficient catalyst for the reduction of organic dyes. The catalytic rate constant is evaluated from the decrease in absorbance of the dye molecules. Presence of cationic or anionic surfactants greatly influences the catalytic reaction. The other factors like hydrophobicity of the organic dyes, complex formation of the dyes with anionic surfactants, repulsion between dyes and cationic surfactant, adsorption of dyes on the Au NPs also play important role on the reaction rate.

Biosorption of six basic and acidic dyes on brown alga Sargassum ilicifolium: optimization, kinetic and isotherm studies.

PubMed

Tabaraki, Reza; Sadeghinejad, Negar

2017-06-01

Biosorption of Methyl Blue (MB), Fuchsin Acid (FA), Rhodamine B (RB), Methylene Blue (MEB), Bromocresol purple (BC) and Methyl Orange (MO) onto Sargassum ilicifolium was studied in a batch system. Effect of dye structure on biosorption by Sargassum ilicifolium was studied to define the correlation between chemical structure and biosorption capacity. Different dye groups such as triarylmethane (MB, FA and BC), monoazo (MO), thiazine (MEB) and xanthene (RB) were studied. At optimum experimental conditions for each dye, biosorption capacity was determined and compared. The results indicate that the chemical structure (triarylmethane, monoazo, thiazine, xanthene), number of sulfonic groups, basicity (element of chromophore group: S, N, O) and molecular weight of dye molecules influence their biosorption capacity. Experimental parameters such as biosorbent dose, pH, contact time, and initial dye concentration were optimized for each dye. The biosorption kinetic data were successfully described by the pseudo second-order model. The biosorption results were also analyzed by the Langmuir and Freundlich isotherms. Finally, biosorption capacities obtained using Sargassum ilicifolium were compared with the ones presented in the literature.

Improved stability and electrophoretic properties of preformed fluorescent cationic dye-DNA complexes in a taps-tetrapentylammonium buffer in agarose slab gels.

PubMed

Zeng, Z; Clark, S M; Mathies, R A; Glazer, A N

1997-10-01

High-resolution capillary electrophoresis sizing of preformed complexes of bis-intercalating fluorescent dyes with double-stranded DNA has been demonstrated using hydroxyethylcellulose and 3-[tris-(hydroxymethyl) methylamino]-1-propanesulfonic acid-tetrapentylammonium (Taps-NPe+4) buffers (S. M. Clark and R. A. Mathies, Anal. Chem. 69, 1355-1363, 1997). Such capillary electrophoresis separations were unattainable in conventional buffers containing other cations such as Tris+, Na+, and NH+4. We report here the behavior of preformed double-stranded DNA-dye complexes on agarose slab gel electrophoresis in 40 mM Taps-NPe+4, 1 mM H2EDTA, pH 8.2. Upon electrophoresis in this buffer (a) complexes formed at DNA base pairs:dye ratios ranging from 100:1 to 5:1 show the same mobility; (b) the half-lives of DNA-dye complexes with monointercalators are two- to threefold longer than those in commonly used Tris buffers; (c) there is little dye transfer between labeled and unlabeled DNA molecules; and (d) precise two-color sizing of preformed restriction fragment-dye complexes with fluorescent bisintercalators is achieved.

Effect of the annealing temperature and ion-beam bombardment on the properties of solution-derived HfYGaO films as liquid crystal alignment layers

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

Park, Hong-Gyu; Lee, Yun-Gun; Jang, Sang Bok

2015-11-15

Hafnium yttrium gallium oxide (HfYGaO) films were applied to liquid crystal displays (LCDs) as liquid crystal (LC) alignment layers, replacing conventional polyimide (PI) layers. The HfYGaO alignment layers were prepared by fabricating solution-processed HfYGaO films, annealing them, and treating them with ion-beam (IB) irradiation. The authors studied the effects of annealing temperature and IB irradiation of the solution-derived HfYGaO films on the orientation of LC molecules. The LC molecules on the solution-derived HfYGaO films were homogeneously and uniformly aligned by IB irradiation, irrespective of the annealing temperature. Atomic force microscopy analyses revealed that the surface reformation of the HfYGaO filmsmore » induced by IB irradiation strengthened the van der Waals force between the LC molecules and the HfYGaO films, leading to uniform LC alignment. Enhanced electro-optical characteristics were observed in the twisted-nematic (TN) LCDs based on IB-irradiated HfYGaO films compared with those of TN-LCDs based on PI layers, demonstrating the high application potential of the proposed solution-derived HfYGaO films as LC alignment layers.« less

Dyes and Redox Couples with Matched Energy Levels: Elimination of the Dye-Regeneration Energy Loss in Dye-Sensitized Solar Cells.

PubMed

Jiang, Dianlu; Darabedian, Narek; Ghazarian, Sevak; Hao, Yuanqiang; Zhgamadze, Maxim; Majaryan, Natalie; Shen, Rujuan; Zhou, Feimeng

2015-11-16

In dye-sensitized solar cells (DSSCs), a significant dye-regeneration force (ΔG(reg)(0)≥0.5 eV) is usually required for effective dye regeneration, which results in a major energy loss and limits the energy-conversion efficiency of state-of-art DSSCs. We demonstrate that when dye molecules and redox couples that possess similar conjugated ligands are used, efficient dye regeneration occurs with zero or close-to-zero driving force. By using Ru(dcbpy)(bpy)2(2+) as the dye and Ru(bpy)2(MeIm)2(3+//2+) as the redox couple, a short-circuit current (J(sc)) of 4 mA cm(-2) and an open-circuit voltage (V(oc)) of 0.9 V were obtained with a ΔG(reg)(0) of 0.07 eV. The same was observed for the N3 dye and Ru(bpy)2(SCN)2(1+/0) (ΔG(reg)(0)=0.0 eV), which produced an J(sc) of 2.5 mA cm(-2) and V(oc) of 0.6 V. Charge recombination occurs at pinholes, limiting the performance of the cells. This proof-of-concept study demonstrates that high V(oc) values can be attained by significantly curtailing the dye-regeneration force. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Crystallization of Stretched Polyimides: A Structure-Property Study

NASA Technical Reports Server (NTRS)

Hinkley, Jeffrey A.; Dezern, James F.

2002-01-01

A simple rotational isomeric state model was used to detect the degree to which polyimide repeat units might align to give an extended crystal. It was found experimentally that the hallmarks of stretch-crystallization were more likely to occur in materials whose molecules could readily give extended, aligned conformations. A proposed screening criterion was 84% accurate in selecting crystallizing molecules.

Methods for immobilizing nucleic acids on a gel substrate

DOEpatents

Mirzabekov, Andrei Darievich; Proudnikov, Dimitri Y.; Timofeev, Edward N.; Kochetkova, Svetlana V.; Florentiev, Vladimir L.; Shick, Valentine V.

1999-01-01

A method for labeling oligonucleotide molecules, and for immobilizing oligonucleotide and DNA molecules is provided comprising modifying the molecules to create a chemically active group, and contacting activated fluorescent dyes to the region. A method for preparing an immobilization substrate is also provided comprising modifying a gel to contain desired functional groups which covalently interact with certain moieties of the oligonucleotide molecules. A method for immobilizing biomolecules and other molecules within a gel by copolymerization of allyl-substituted oligonucleotides, DNA and proteins with acrylamide is also provided.

Structure Prediction of Self-Assembled Dye Aggregates from Cryogenic Transmission Electron Microscopy, Molecular Mechanics, and Theory of Optical Spectra.

PubMed

Friedl, Christian; Renger, Thomas; Berlepsch, Hans V; Ludwig, Kai; Schmidt Am Busch, Marcel; Megow, Jörg

2016-09-01

Cryogenic transmission electron microscopy (cryo-TEM) studies suggest that TTBC molecules self-assemble in aqueous solution to form single-walled tubes with a diameter of about 35 Å. In order to reveal the arrangement and mutual orientations of the individual molecules in the tube, we combine information from crystal structure data of this dye with a calculation of linear absorbance and linear dichroism spectra and molecular dynamics simulations. We start with wrapping crystal planes in different directions to obtain tubes of suitable diameter. This set of tube models is evaluated by comparing the resulting optical spectra with experimental data. The tubes that can explain the spectra are investigated further by molecular dynamics simulations, including explicit solvent molecules. From the trajectories of the most stable tube models, the short-range ordering of the dye molecules is extracted and the optimization of the structure is iteratively completed. The final structural model is a tube of rings with 6-fold rotational symmetry, where neighboring rings are rotated by 30° and the transition dipole moments of the chromophores form an angle of 74° with respect to the symmetry axis of the tube. This model is in agreement with cryo-TEM images and can explain the optical spectra, consisting of a sharp red-shifted J-band that is polarized parallel to to the symmetry axis of the tube and a broad blue-shifted H-band polarized perpendicular to this axis. The general structure of the homogeneous spectrum of this hybrid HJ-aggregate is described by an analytical model that explains the difference in redistribution of oscillator strength inside the vibrational manifolds of the J- and H-bands and the relative intensities and excitation energies of those bands. In addition to the particular system investigated here, the present methodology can be expected to aid the structure prediction for a wide range of self-assembled dye aggregates.

An easy and effective method for the intercalation of hydrophobic natural dye into organo-montmorillonite for improved photostability

NASA Astrophysics Data System (ADS)

Taguchi, Taiga; Kohno, Yoshiumi; Shibata, Masashi; Tomita, Yasumasa; Fukuhara, Choji; Maeda, Yasuhisa

2018-05-01

β-carotene (BC) is one of the naturally occurring dyes belonging to the carotenoids group. Although it is more environmentally friendly and better suited for humans compared with synthetic dyes, it destabilizes with light and heat, easily losing its color under irradiation. Extended application of BC are therefore limited. The aim of this study is to improve the stability of BC by intercalation into the montmorillonite layers modified with a cationic surfactant, by a simple mixing and minimal solvent use. The physical mixing of small quantities of concentrated BC/hexane solutions with organo-modified montmorillonite successfully resulted in the composite material. The length and the number of alkyl chains of the surfactant used for the organic modification influenced the stability enhancement of the incorporated dye. The improved stability of the dye molecules incorporated in the interlayer space was found to be due to restricted contact with atmospheric oxygen.

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

Yen, Chih-Ping; Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan; Yu, Pin-Feng

The deposition of various distinct organic dyes, including ruthenium complex N3, melanin nanoparticle (MNP), and porphyrin-based donor-π-acceptor dye YD2-o-C8, by using matrix-assisted pulsed laser evaporation (MAPLE) for application to dye-sensitized solar cell (DSSC) is investigated systematically. It is found that the two covalently-bonded organic molecules, i.e., MNP and YD2-o-C8, can be transferred from the frozen target to the substrate with maintained molecular integrity. In contrast, N3 disintegrates in the process, presumably due to the lower bonding strength of metal complex compared to covalent bond. With the method, DSSC using YD2-o-C8 is fabricated, and an energy conversion efficiency of 1.47% ismore » attained. The issue of the low penetration depth of dyes deposited by MAPLE and the possible resolution to it are studied. This work demonstrates that MAPLE could be an alternative way for deposition of organic dyes for DSSC.« less

New physicochemical interpretations for the adsorption of food dyes on chitosan films using statistical physics treatment.

PubMed

Dotto, G L; Pinto, L A A; Hachicha, M A; Knani, S

2015-03-15

In this work, statistical physics treatment was employed to study the adsorption of food dyes onto chitosan films, in order to obtain new physicochemical interpretations at molecular level. Experimental equilibrium curves were obtained for the adsorption of four dyes (FD&C red 2, FD&C yellow 5, FD&C blue 2, Acid Red 51) at different temperatures (298, 313 and 328 K). A statistical physics formula was used to interpret these curves, and the parameters such as, number of adsorbed dye molecules per site (n), anchorage number (n'), receptor sites density (NM), adsorbed quantity at saturation (N asat), steric hindrance (τ), concentration at half saturation (c1/2) and molar adsorption energy (ΔE(a)) were estimated. The relation of the above mentioned parameters with the chemical structure of the dyes and temperature was evaluated and interpreted. Copyright © 2014 Elsevier Ltd. All rights reserved.

Application of Synthetic Layered Sodium Silicate Magadiite Nanosheets for Environmental Remediation of Methylene Blue Dye in Water

PubMed Central

2017-01-01

The removal of methylene blue (MB) dye from water was investigated using synthetic nano-clay magadiite (SNCM). SNCM was synthesized by a hydrothermal treatment under autogenous pressure. A rosette-shaped single mesoporous magadiite phase with 16.63 nm average crystallite size and 33 m2∙g−1 Braunauer-Emmet-Teller (BET)-surface area was recorded. The adsorption results indicated the pronounced affinity of the SNCM to the MB dye molecules, which reached an adsorption uptake of 20.0 mg MB dye/g of SNCM. The elimination of MB dye by the SNCM was kinetically and thermodynamically considered; a pseudo-second-order kinetic model was attained, and its spontaneous, chemical, and endothermic nature was verified. SNCM was shown to be robust without a detectable reduction in the adsorption capacity after up to four times re-use. PMID:28773120

Peripheral Hole Acceptor Moieties on an Organic Dye Improve Dye‐Sensitized Solar Cell Performance

PubMed Central

Hao, Yan; Gabrielsson, Erik; Lohse, Peter William; Yang, Wenxing; Johansson, Erik M. J.; Hagfeldt, Anders

2015-01-01

Investigation of charge transfer dynamics in dye‐sensitized solar cells is of fundamental interest and the control of these dynamics is a key factor for developing more efficient solar cell devices. One possibility for attenuating losses through recombination between injected electrons and oxidized dye molecules is to move the positive charge further away from the metal oxide surface. For this purpose, a metal‐free dye named E6 is developed, in which the chromophore core is tethered to two external triphenylamine (TPA) units. After photoinduced electron injection into TiO2, the remaining hole is rapidly transferred to a peripheral TPA unit. Electron–hole recombination is slowed down by 30% compared to a reference dye without peripheral TPA units. Furthermore, it is found that the added TPA moieties improve the electron blocking effect of the dye, retarding recombination of electrons from TiO2 to the cobalt‐based electrolyte. PMID:27722076

Thermally and optically tunable lasing properties from dye-doped holographic polymer dispersed liquid crystal in capillaries

NASA Astrophysics Data System (ADS)

Chen, Maozhou; Dai, Haitao; Wang, Dongshuo; Yang, Yue; Luo, Dan; Zhang, Xiaodong; Liu, Changlong

2018-03-01

In this paper, we investigated tunable lasing properties from the dye-doped holographic polymer dispersed liquid crystal (HPDLC) gratings in capillaries with thermal and optical manners. The thermally tunable range of the lasing from the dye-doped HPDLC reached 8.60 nm with the temperature ranging from 23 °C to 50 °C. The optically tunable laser emission was achieved by doping azo-dye in HPDLC. The transition of azo-dye from trans- to cis-state could induce the reorientation of LC molecules after UV light irradiation, which resulted in the variation of refractive index contrast of LC-rich/polymer-rich layer in HPDLC. Experimentally, the emission wavelength of lasing showed a blueshift (about 2 nm) coupled with decreasing output intensities. The tunable laser based on HPDLC may enable more applications in laser displays, optical communication, biosensors, etc.

Dye-doped silica-based nanoparticles for bioapplications

NASA Astrophysics Data System (ADS)

Nhung Tran, Hong; Nghiem, Thi Ha Lien; Thuy Duong Vu, Thi; Tan Pham, Minh; Van Nguyen, Thi; Trang Tran, Thu; Chu, Viet Ha; Thuan Tong, Kim; Thuy Tran, Thanh; Le, Thi Thanh Xuan; Brochon, Jean-Claude; Quy Nguyen, Thi; Nhung Hoang, My; Nguyen Duong, Cao; Thuy Nguyen, Thi; Hoang, Anh Tuan; Hoa Nguyen, Phuong

2013-12-01

This paper presents our recent research results on synthesis and bioapplications of dye-doped silica-based nanoparticles. The dye-doped water soluble organically modified silicate (ORMOSIL) nanoparticles (NPs) with the size of 15-100 nm were synthesized by modified Stöber method from methyltriethoxysilane CH3Si(OCH3)3 precursor (MTEOS). Because thousands of fluorescent dye molecules are encapsulated in the silica-based matrix, the dye-doped nanoparticles are extremely bright and photostable. Their surfaces were modified with bovine serum albumin (BSA) and biocompatible chemical reagents. The highly intensive luminescent nanoparticles were combined with specific bacterial and breast cancer antigen antibodies. The antibody-conjugated nanoparticles can identify a variety of bacterium, such as Escherichia coli O157:H7, through antibody-antigen interaction and recognition. A highly sensitive breast cancer cell detection has been achieved with the anti-HER2 monoclonal antibody-nanoparticles complex. These results demonstrate the potential to apply these fluorescent nanoparticles in various biodetection systems.

Quantum chemical calculations, molecular dynamic (MD) simulations and experimental studies of using some azo dyes as corrosion inhibitors for iron. Part 2: Bis-azo dye derivatives

NASA Astrophysics Data System (ADS)

Madkour, Loutfy H.; Kaya, Savaş; Guo, Lei; Kaya, Cemal

2018-07-01

The adsorption behavior and inhibition mechanism of five synthesized bis-azo dye (BAD) derivatives on the corrosion of iron in aerated HNO3 and NaOH were investigated by performing potentiostatic polarization, weight loss (WL), thermometric and UV-visible spectra measurements. DFT calculations is applied to study the correlation between corrosion inhibition and global reactivity descriptors such as: EHOMO, ELUMO, molecular gap (ΔE), the dipole moment (μ), the global hardness (η), softness(S), electronegativity (χ), proton affinity (PA), electrophilicity (ω), nucleophilicity (ɛ), electrons transferred from inhibitors to metal surface (ΔN), initial molecule-metal interaction energy (Δψ), total electronic energy (E) and the energy change during electronic back-donation process (ΔEb-d). To mimic the real environment of corrosion inhibition, molecular dynamic (MD) simulations in aqueous phase have also been modelled consisting of all concerned species (inhibitor molecule, H2O, H3O+ ion, NO3- ion, OH- and Fe surface). The results confirmed that BAD molecules inhibit iron by adsorption behavior through donating and accepting electrons together with the formation of [Fe (II) and Fe (III)-BAD] chelate complex compounds. BAD's behavior is mainly chemisorption with some physisorption obeyed Frumkin and that of El-Awady adsorption isotherm. Kinetic parameters such as: (Kb, 1/y, Kads, f, ΔG°ads) have been determined and discussed. Binding energies of BAD molecules on Fe (110) surface followed the order: BAD_ 2 > BAD_ 1 > BAD_ 3 > BAD_ 4 > BAD_ 5. Theoretical results were found to be consistent with the experimental data reported. Our results provide important atomic/molecular insights into the anticorrosive mechanism of inhibitor molecules, which could help in understanding the organic-metal interface and designing more appropriate organic corrosion inhibitors.

Localization microscopy of DNA in situ using Vybrant{sup ®} DyeCycle™ Violet fluorescent probe: A new approach to study nuclear nanostructure at single molecule resolution

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

Żurek-Biesiada, Dominika; Szczurek, Aleksander T.; Prakash, Kirti

Higher order chromatin structure is not only required to compact and spatially arrange long chromatids within a nucleus, but have also important functional roles, including control of gene expression and DNA processing. However, studies of chromatin nanostructures cannot be performed using conventional widefield and confocal microscopy because of the limited optical resolution. Various methods of superresolution microscopy have been described to overcome this difficulty, like structured illumination and single molecule localization microscopy. We report here that the standard DNA dye Vybrant{sup ®} DyeCycle™ Violet can be used to provide single molecule localization microscopy (SMLM) images of DNA in nuclei ofmore » fixed mammalian cells. This SMLM method enabled optical isolation and localization of large numbers of DNA-bound molecules, usually in excess of 10{sup 6} signals in one cell nucleus. The technique yielded high-quality images of nuclear DNA density, revealing subdiffraction chromatin structures of the size in the order of 100 nm; the interchromatin compartment was visualized at unprecedented optical resolution. The approach offers several advantages over previously described high resolution DNA imaging methods, including high specificity, an ability to record images using a single wavelength excitation, and a higher density of single molecule signals than reported in previous SMLM studies. The method is compatible with DNA/multicolor SMLM imaging which employs simple staining methods suited also for conventional optical microscopy. - Highlights: • Super-resolution imaging of nuclear DNA with Vybrant Violet and blue excitation. • 90nm resolution images of DNA structures in optically thick eukaryotic nuclei. • Enhanced resolution confirms the existence of DNA-free regions inside the nucleus. • Optimized imaging conditions enable multicolor super-resolution imaging.« less

Alignment of RNA molecules: Binding energy and statistical properties of random sequences

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

Valba, O. V., E-mail: valbaolga@gmail.com; Nechaev, S. K., E-mail: sergei.nechaev@gmail.com; Tamm, M. V., E-mail: thumm.m@gmail.com

2012-02-15

A new statistical approach to the problem of pairwise alignment of RNA sequences is proposed. The problem is analyzed for a pair of interacting polymers forming an RNA-like hierarchical cloverleaf structures. An alignment is characterized by the numbers of matches, mismatches, and gaps. A weight function is assigned to each alignment; this function is interpreted as a free energy taking into account both direct monomer-monomer interactions and a combinatorial contribution due to formation of various cloverleaf secondary structures. The binding free energy is determined for a pair of RNA molecules. Statistical properties are discussed, including fluctuations of the binding energymore » between a pair of RNA molecules and loop length distribution in a complex. Based on an analysis of the free energy per nucleotide pair complexes of random RNAs as a function of the number of nucleotide types c, a hypothesis is put forward about the exclusivity of the alphabet c = 4 used by nature.« less

Spatial variation of electrode position in bioelectrochemical treatment system: Design consideration for azo dye remediation.

PubMed

Yeruva, Dileep Kumar; Shanthi Sravan, J; Butti, Sai Kishore; Annie Modestra, J; Venkata Mohan, S

2018-05-01

In the present study, three bio-electrochemical treatment systems (BET) were designed with variations in cathode electrode placement [air exposed (BET1), partially submerged (BET2) and fully submerged (BET3)] to evaluate azo-dye based wastewater treatment at three dye loading concentrations (50, 250 and 500 mg L -1 ). Highest dye decolorization (94.5 ± 0.4%) and COD removal (62.2 ± 0.8%) efficiencies were observed in BET3 (fully submerged electrodes) followed by BET1 and BET2, while bioelectrogenic activity was highest in BET1 followed by BET2 and BET3. It was observed that competition among electron acceptors (electrode, dye molecules and intermediates) critically regulated the fate of bio-electrogenesis to be higher in BET1 and dye removal higher in BET3. Maximum half-cell potentials in BET3 depict higher electron acceptance by electrodes utilized for dye degradation. Study infers that spatial positioning of electrodes in BET3 is more suitable towards dye remediation, which can be considered for scaling-up/designing a treatment plant for large-scale industrial applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Molecular surface area based predictive models for the adsorption and diffusion of disperse dyes in polylactic acid matrix.

PubMed

Xu, Suxin; Chen, Jiangang; Wang, Bijia; Yang, Yiqi

2015-11-15

Two predictive models were presented for the adsorption affinities and diffusion coefficients of disperse dyes in polylactic acid matrix. Quantitative structure-sorption behavior relationship would not only provide insights into sorption process, but also enable rational engineering for desired properties. The thermodynamic and kinetic parameters for three disperse dyes were measured. The predictive model for adsorption affinity was based on two linear relationships derived by interpreting the experimental measurements with molecular structural parameters and compensation effect: ΔH° vs. dye size and ΔS° vs. ΔH°. Similarly, the predictive model for diffusion coefficient was based on two derived linear relationships: activation energy of diffusion vs. dye size and logarithm of pre-exponential factor vs. activation energy of diffusion. The only required parameters for both models are temperature and solvent accessible surface area of the dye molecule. These two predictive models were validated by testing the adsorption and diffusion properties of new disperse dyes. The models offer fairly good predictive ability. The linkage between structural parameter of disperse dyes and sorption behaviors might be generalized and extended to other similar polymer-penetrant systems. Copyright © 2015 Elsevier Inc. All rights reserved.

Optimization of Biosorptive Removal of Dye from Aqueous System by Cone Shell of Calabrian Pine

PubMed Central

Deniz, Fatih

2014-01-01

The biosorption performance of raw cone shell of Calabrian pine for C.I. Basic Red 46 as a model azo dye from aqueous system was optimized using Taguchi experimental design methodology. L9 (33) orthogonal array was used to optimize the dye biosorption by the pine cone shell. The selected factors and their levels were biosorbent particle size, dye concentration, and contact time. The predicted dye biosorption capacity for the pine cone shell from Taguchi design was obtained as 71.770 mg g−1 under optimized biosorption conditions. This experimental design provided reasonable predictive performance of dye biosorption by the biosorbent (R 2: 0.9961). Langmuir model fitted better to the biosorption equilibrium data than Freundlich model. This displayed the monolayer coverage of dye molecules on the biosorbent surface. Dubinin-Radushkevich model and the standard Gibbs free energy change proposed physical biosorption for predominant mechanism. The logistic function presented the best fit to the data of biosorption kinetics. The kinetic parameters reflecting biosorption performance were also evaluated. The optimization study revealed that the pine cone shell can be an effective and economically feasible biosorbent for the removal of dye. PMID:25405213

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

Lucky Imaging: Improved Localization Accuracy for Single Molecule Imaging

PubMed Central

Cronin, Bríd; de Wet, Ben; Wallace, Mark I.

2009-01-01

We apply the astronomical data-analysis technique, Lucky imaging, to improve resolution in single molecule fluorescence microscopy. We show that by selectively discarding data points from individual single-molecule trajectories, imaging resolution can be improved by a factor of 1.6 for individual fluorophores and up to 5.6 for more complex images. The method is illustrated using images of fluorescent dye molecules and quantum dots, and the in vivo imaging of fluorescently labeled linker for activation of T cells. PMID:19348772

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.

Extended Fluorescent Resonant Energy Transfer in DNA Constructs

NASA Astrophysics Data System (ADS)

Oh, Taeseok

This study investigates the use of surfactants and metal cations for the enhancement of long range fluorescent resonant energy transfer (FRET) and the antenna effect in DNA structures with multiple fluorescent dyes. Double-stranded (ds) DNA structures were formed by hybridization of 21mer DNA oligonucleotides with different arrangements of three fluorescent TAMRA donor dyes with two different complementary 21mer oligonucleotides with one fluorescent TexasRed acceptor dye. In such DNA structures, hydrophobic interactions between the fluorescent dyes in close proximity produces dimerization which along with other quenching mechanisms leads to significant reduction of fluorescent emission properties. Addition of the surfactants Triton X-100, cetyltrimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) along with sodium cations (Na+) and divalent magnesium cations (Mg 2+) were tested for their ability to reduce quenching of the fluorescent dyes and improve overall fluorescent emission, the long range FRET and the antenna effect properties. When the neutral (uncharged) surfactant Triton X-100 was added to the FRET ds-DNA hybrid structures with three TAMRA donors and one TexasRed acceptor, dye dimerization and emission quenching remained unaffected. However, for the positively charged CTAB surfactant at concentrations of 100 uM or higher, the neutralization of the negatively charged ds-DNA backbone by the cationic surfactant micelles was found to reduce TAMRA dye dimerization and emission quenching and improve TexasRed quantum yield, resulting in much higher FRET efficiencies and an enhanced antenna effect. This improvement is likely due to the CTAB molecules covering or sheathing the fluorescent donor and acceptor dyes which breaks up the dimerized dye complexes and prevents further quenching from interactions with water molecules and guanine bases in the DNA structure. While the negatively charged SDS surfactant alone was not able to reduce dimerization and emission quenching due to repulsive forces between DNA and SDS micelles, the addition of cations such as sodium ions (Na+) and divalent magnesium ions (Mg2+) did lead to a significant reduction in the dimerization and emission quenching resulting in much higher FRET efficiency and an enhanced antenna effect. It appears that when the repulsive electrostatic forces are screened by the cations (Mg2+ in particular), the SDS micelles can approach the FRET ds-DNA structures thereby sheathing or insulating the TAMRA and TexasRed dyes. Overall, the study provides a viable strategy for using combinations of surfactants and cations to reduce adverse fluorescent dye and other quenching mechanisms and improve the overall long distance FRET efficiency and the antenna effect in DNA structures with multi-donor and single acceptor fluorescent dye groups.

Nanofabricated Racks of Aligned and Anchored DNA Substrates for Single-Molecule Imaging

PubMed Central

2009-01-01

Single-molecule studies of biological macromolecules can benefit from new experimental platforms that facilitate experimental design and data acquisition. Here we develop new strategies to construct curtains of DNA in which the molecules are aligned with respect to one another and maintained in an extended configuration by anchoring both ends of the DNA to the surface of a microfluidic sample chamber that is otherwise coated with an inert lipid bilayer. This “double-tethered” DNA substrate configuration is established through the use of nanofabricated rack patterns comprised of two distinct functional elements: linear barriers to lipid diffusion that align DNA molecules anchored by one end to the bilayer and antibody-coated pentagons that provide immobile anchor points for the opposite ends of the DNA. These devices enable the alignment and anchoring of thousands of individual DNA molecules, which can then be visualized using total internal reflection fluorescence microscopy under conditions that do not require continuous application of buffer flow to stretch the DNA. This unique strategy offers the potential for studying protein−DNA interactions on large DNA substrates without compromising measurements through application of hydrodynamic force. We provide a proof-of-principle demonstration that double-tethered DNA curtains made with nanofabricated rack patterns can be used in a one-dimensional diffusion assay that monitors the motion of quantum dot-tagged proteins along DNA. PMID:19736980

Nanofabricated racks of aligned and anchored DNA substrates for single-molecule imaging.

PubMed

Gorman, Jason; Fazio, Teresa; Wang, Feng; Wind, Shalom; Greene, Eric C

2010-01-19

Single-molecule studies of biological macromolecules can benefit from new experimental platforms that facilitate experimental design and data acquisition. Here we develop new strategies to construct curtains of DNA in which the molecules are aligned with respect to one another and maintained in an extended configuration by anchoring both ends of the DNA to the surface of a microfluidic sample chamber that is otherwise coated with an inert lipid bilayer. This "double-tethered" DNA substrate configuration is established through the use of nanofabricated rack patterns comprised of two distinct functional elements: linear barriers to lipid diffusion that align DNA molecules anchored by one end to the bilayer and antibody-coated pentagons that provide immobile anchor points for the opposite ends of the DNA. These devices enable the alignment and anchoring of thousands of individual DNA molecules, which can then be visualized using total internal reflection fluorescence microscopy under conditions that do not require continuous application of buffer flow to stretch the DNA. This unique strategy offers the potential for studying protein-DNA interactions on large DNA substrates without compromising measurements through application of hydrodynamic force. We provide a proof-of-principle demonstration that double-tethered DNA curtains made with nanofabricated rack patterns can be used in a one-dimensional diffusion assay that monitors the motion of quantum dot-tagged proteins along DNA.

Recent advances based on the synergetic effect of adsorption for removal of dyes from waste water using photocatalytic process.

PubMed

Natarajan, Subramanian; Bajaj, Hari C; Tayade, Rajesh J

2018-03-01

The problem of textile dye pollution has been addressed by various methods, mainly physical, chemical, biological, and acoustical. These methods mainly separate and/or remove the dye present in water. Recently, advanced oxidation processes (AOP) have been focused for removal of dye from waste water due to their advantages such as ecofriendly, economic and capable to degrade many dyes or organic pollutant present in water. Photocatalysis is one of the advance oxidation processes, mainly carried out under irradiation of light and suitable photocatalytic materials. The photocatalytic activity of the photocatalytic materials mainly depends on the band gap, surface area, and generation of electron-hole pair for degradation dyes present in water. It has been observed that the surface area plays a major role in photocatalytic degradation of dyes, by providing higher surface area, which leads to the higher adsorption of dye molecule on the surface of photocatalyst and enhances the photocatalytic activity. This present review discusses the synergic effect of adsorption of dyes on the photocatalytic efficiency of various nanostructured high surface area photocatalysts. In addition, it also provides the properties of the water polluting dyes, their mechanism and various photocatalytic materials; and their morphology used for the dye degradation under irradiation of light along with the future prospects of highly adsorptive photocatalytic material and their application in photocatalytic removal of dye from waste water. Copyright © 2017. Published by Elsevier B.V.

Mesoporous inverse opal TiO2 film as light scattering layer for dye-sensitized solar cell.

PubMed

Jin, Mingshi; Kim, Sung Soo; Yoon, Minyoung; Li, Zhenghua; Lee, Yoon Yun; Kim, Ji Man

2012-01-01

The light harvesting efficiency of dye-sensitized solar cells was enhanced by using a scattering layer. Such as sphere type TiO2, inverse photonic crystal TiO2, hollow spherical TiO2. Among these materials, the TiO2 with inverse photonic crystal (IPC) structure, synthesized by self-assembly using spherical templates, has attracted much attention due to their photonic crystal characteristics and light scattering effects. However, when applied in the DSSCs, the surface area of IPC is very low that caused insufficient adsorption amount of dye molecules. In the present work, a scattering layer with mesoporous inverse photonic crystal (MIPC) TiO2 film was fabricated by the sol-gel reactions with surfactant-assisted sol-gel method using poly(methyl methacrylate) as the template and titanium (IV) isopropoxide as the TiO2 precursor. After removing the PMMA and surfactant, a highly ordered macroporous structure with mesopores were successfully obtained. The surface area and total pore volume of the MIPC were 82 m2/g and 0.31 cm3/g, respectively, which is much larger than those of the IPC. The DSSCs with the scattering layer of MIPC film exhibited 18 and 10% higher photo-conversion efficiency than those of cells only with a nano-crystalline TiO2 film and with scattering layer of IPC film. From UV-visible spectra of dye solutions, the MIPC film showed a higher amount of absorbed dye molecules than those of the reference and IPC films. Accordingly, an increase in the photo-current density through abundant adsorption of the dye, coupled with inherent light scattering ability can improve overall photo-conversion efficiency.

Brooker's merocyanine: Comparison of single crystal structures

NASA Astrophysics Data System (ADS)

Hayes, Kathleen L.; Lasher, Emily M.; Choczynski, Jack M.; Crisci, Ralph R.; Wong, Calvin Y.; Dragonette, Joseph; Deschner, Joshua; Cardenas, Allan Jay P.

2018-06-01

Brooker's merocyanine and its derivatives are well-studied molecules due to their very interesting optical properties. Merocyanine dyes exhibit different colors in solution depending on the solvent's polarity, pH, aggregation and intermolecular interactions. The synthesis of 1-methyl-4-[(oxocyclohexadienylidene)ethylidene]-1,4-dihydropyridine (MOED) dye yielded a particularly interesting solid state structure where in one crystal lattice, MOED and its protonated form are bound by hydrogen bonding interactions.

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.

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.

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

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.

The effect of surfactant on pollutant biosorption of Trametes versicolor

NASA Astrophysics Data System (ADS)

Gül, Ülküye Dudu; Silah, Hülya; Akbaş, Halide; Has, Merve

2016-04-01

The major problem concerning industrial wastewater is treatment of dye and heavy metal containing effluents. Industrial effluents are also contained surfactants that are used as levelling, dispersing and wetting agents. The purpose of this study was to investigate the effect of surfactant on textile dye biosorption properties of a white rot fungus named Trametes versicolor. Reactive dyes are commonly used in textile industry because of their advantages such as brightness and excellent color fastness. A recative textile dye, called Everzol Black, was used in this study. The low-cost mollasses medium is used for fungal growth. The usage of mollases, the sugar refinery effluent as a source of energy and nutrients, gained importance because of reducing the cost and also reusing another waste. In biosorption process the effect of surfactant on dye removal properties of T. versicolor was examined as a function of pH, dye consentration and surfactant concentration. The results of this study showed that the surfactant enhanced the dye removal capacity of Trametes versicolor. The dye and surfactant molecules were interacted electrostatically and these electrostatic interactions improved dye removal properties of filamentous fungus T. versicolor. The results of this study recommended the use of surfactants as an inducer in textile wastewater treatment technologies.

The melting of native domain structure in effector activation of IgG studied by using congo red as a specific probe.

PubMed

Piekarska, B; Roterman, I; Rybarska, J; Koniczny, L; Kaszuba, J

1994-03-01

The nature of structural changes in IgG molecules associated with the binding to antigen and/or heat aggregation was studied using bis azo dye (Congo Red) as the specific probe. It was found, that protein conformation responsible for binding the dye represents an unfolding intermediate with properties corresponding to a molten globule state. The properties of the dye-protein complex reveal the signs of an unfolding of the peptide chain with simultaneously preserved relatively compact packing. Immunoglobulins which were induced by heating, or binding to antigen in order to form the complex with dye ligands, become more susceptible for digestion. The main peptide of molecular weight 30,000 D which appears in products was suggested to originate from a heavy chain after its splitting in the region of CH1 domain. The energetic evaluation of stability of IgG domains also indicates that CH1 is the least stable fragment of the heavy chain and its conformation may be destabilized first. It was concluded that destabilized tertiary packing of antibodies bound to antigen may favour the association of closely situated immunoglobulin molecules increasing the stability of the immune complex and influencing in the result its effector activity.

Dye adsorption onto activated carbons from tyre rubber waste using surface coverage analysis.

PubMed

Mui, Edward L K; Cheung, W H; Valix, Marjorie; McKay, Gordon

2010-07-15

Two types of activated carbons from tyre char (with or without sulphuric acid treatment) were produced via carbon dioxide activation with BET surface areas in the range 59-1118 m(2)/g. Other characterisation tests include micropore and mesopore surface areas and volumes, pH, and elemental compositions, particularly heteroatoms such as nitrogen and sulphur. They were correlated to the adsorption capacity which were in the range of 0.45-0.71 mmol/g (untreated) and 0.62-0.84 mmol/g (acid-treated) for Acid Blue 25. In the case of larger-sized molecules like Acid Yellow 117, capacities were in the range of 0.23-0.42 mmol/g (untreated) and 0.29-0.40 mmol/g (acid-treated). Some tyre carbons exhibit a more superior performance than a microporous, commercial activated carbon (Calgon F400). By modelling the dye adsorption equilibrium data, the Redlich-Peterson isotherm is adopted as it has the lowest SSE. Based on the surface coverage analysis, a novel molecular orientation modelling of adsorbed dyes has been proposed and correlated with surface area and surface charge. For the acid dyes used in this study, molecules were likely to be adsorbed by the mesopore areas. Copyright 2010 Elsevier Inc. All rights reserved.

Activated carbon derived from carbon residue from biomass gasification and its application for dye adsorption: Kinetics, isotherms and thermodynamic studies.

PubMed

Maneerung, Thawatchai; Liew, Johan; Dai, Yanjun; Kawi, Sibudjing; Chong, Clive; Wang, Chi-Hwa

2016-01-01

In this work, activated carbon (AC) as an effective and low-cost adsorbent was successfully prepared from carbon residue (or char, one of the by-products from woody biomass gasification) via physical activation. The surface area of char was significantly increased from 172.24 to 776.46m(2)/g after steam activation at 900°C. The obtained activated carbons were then employed for the adsorption of dye (Rhodamine B) and it was found that activated carbon obtained from steam activation exhibited the highest adsorption capability, which is mainly attributed to the higher surface area and the abundance of hydroxyl (-OH) and carboxyl (-COOH) groups on the activated carbon surface. Moreover, it was also found that the adsorption capability significantly increased under the basic condition, which can be attributed to the increased electrostatic interaction between the deprotonated (negatively charged) activated carbon and dye molecules. Furthermore, the equilibrium data were fitted into different adsorption isotherms and found to fit well with Langmuir model (indicating that dye molecules form monolayer coverage on activated carbon) with a maximum monolayer adsorption capability of 189.83mg/g, whereas the adsorption kinetics followed the pseudo-second-order kinetics. Copyright © 2015 Elsevier Ltd. All rights reserved.

Development of magnetic luminescent core/shell nanocomplex particles with fluorescence using Rhodamine 6G

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

Lee, Hee Uk; Song, Yoon Seok; Park, Chulhwan

2012-12-15

Graphical abstract: Display Omitted Highlights: ► A simple method was developed to synthesize Co-B/SiO{sub 2}/dye/SiO{sub 2} composite particles. ► The magnetic particle shows that highly luminescent and core/shell particles are formed. ► Such core/shell particles can be easily suspended in water. ► The magnetic particles could detect fluorescence for the application of biosensor. -- Abstract: A simple and reproducible method was developed to synthesize a novel class of Co-B/SiO{sub 2}/dye/SiO{sub 2} composite core/shell particles. Using a single cobalt core, Rhodamine 6G of organic dye molecules was entrapped in a silica shell, resulting in core/shell particles of ∼200 nm diameter. Analysesmore » using a variety of techniques such as transmission electron microscopy, X-ray photoelectron spectroscopy, vibration sample magnetometry, confocal laser scanning microscopy, and fluorescence intensity demonstrated that dye molecules were trapped inside the core/shell particles. A photoluminescence investigation showed that highly luminescent and photostable core/shell particles were formed. Such core/shell particles can be easily suspended in water. The synthesized magnetic particles could be used to detect fluorescence on glass substrate arrays for bioassay and biosensor applications.« less

Fe3O4-in-silica super crystal of defined interstices for single protein molecules entrapment under magnetic flux.

PubMed

Ye, Lin; Yu, Chih Hao; Jiang, PengJu; Qiu, Lin; Ng, Olivia T W; Yung, Ken K L; He, Heyong; Tsang, Shik Chi

2010-09-28

Confocal fluorescence demonstrates that single molecules of dye-labelled Cytochrome C or B5 containing paramagnetic Fe(III) can be magnetically placed into the interstices of super-crystal which is composed of three dimensional regular arrays of Fe(3)O(4) nanoparticles.

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 photochemical approach for a fast and self-limited covalent modification of surface supported graphene with photoactive dyes

NASA Astrophysics Data System (ADS)

Sergeeva, Natalia N.; Chaika, Alexander N.; Walls, Brian; Murphy, Barry E.; Walshe, Killian; Martin, David P.; Richards, Billy D. O.; Jose, Gin; Fleischer, Karsten; Aristov, Victor Yu; Molodtsova, Olga V.; Shvets, Igor V.; Krasnikov, Sergey A.

2018-07-01

Herein, we report a simple method for a covalent modification of surface supported graphene with photoactive dyes. Graphene was fabricated on cubic-SiC/Si(001) wafers due to their low cost and suitability for mass-production of continuous graphene fit for electronic applications on millimetre scale. Functionalisation of the graphene surface was carried out in solution via white light induced photochemical generation of phenazine radicals from phenazine diazonium salt. The resulting covalently bonded phenazine-graphene hybrid structure was characterised by scanning tunnelling microscopy (STM) and spectroscopy (STS), Raman spectroscopy and density functional theory (DFT) calculations. It was found that phenazine molecules form an overlayer, which exhibit a short range order with a rectangular unit cell on the graphene surface. DFT calculations based on STM results reveal that molecules are standing up in the overlayer with the maximum coverage of 0.25 molecules per graphene unit cell. Raman spectroscopy and STM results show that the growth is limited to one monolayer of standing molecules. STS reveals that the phenazine-graphene hybrid structure has a band gap of 0.8 eV.

Ensemble and Single-Molecule Studies on Fluorescence Quenching in Transition Metal Bipyridine-Complexes

PubMed Central

Brox, Dominik; Kiel, Alexander; Wörner, Svenja Johanna; Pernpointner, Markus; Comba, Peter; Martin, Bodo; Herten, Dirk-Peter

2013-01-01

Beyond their use in analytical chemistry fluorescent probes continuously gain importance because of recent applications of single-molecule fluorescence spectroscopy to monitor elementary reaction steps. In this context, we characterized quenching of a fluorescent probe by different metal ions with fluorescence spectroscopy in the bulk and at the single-molecule level. We apply a quantitative model to explain deviations from existing standard models for fluorescence quenching. The model is based on a reversible transition from a bright to a dim state upon binding of the metal ion. We use the model to estimate the stability constants of complexes with different metal ions and the change of the relative quantum yield of different reporter dye labels. We found ensemble data to agree widely with results from single-molecule experiments. Our data indicates a mechanism involving close molecular contact of dye and quenching moiety which we also found in molecular dynamics simulations. We close the manuscript with a discussion of possible mechanisms based on Förster distances and electrochemical potentials which renders photo-induced electron transfer to be more likely than Förster resonance energy transfer. PMID:23483966

Highly multiplexed single-cell analysis of formalin-fixed, paraffin-embedded cancer tissue

PubMed Central

Gerdes, Michael J.; Sevinsky, Christopher J.; Sood, Anup; Adak, Sudeshna; Bello, Musodiq O.; Bordwell, Alexander; Can, Ali; Corwin, Alex; Dinn, Sean; Filkins, Robert J.; Hollman, Denise; Kamath, Vidya; Kaanumalle, Sireesha; Kenny, Kevin; Larsen, Melinda; Lazare, Michael; Lowes, Christina; McCulloch, Colin C.; McDonough, Elizabeth; Pang, Zhengyu; Rittscher, Jens; Santamaria-Pang, Alberto; Sarachan, Brion D.; Seel, Maximilian L.; Seppo, Antti; Shaikh, Kashan; Sui, Yunxia; Zhang, Jingyu; Ginty, Fiona

2013-01-01

Limitations on the number of unique protein and DNA molecules that can be characterized microscopically in a single tissue specimen impede advances in understanding the biological basis of health and disease. Here we present a multiplexed fluorescence microscopy method (MxIF) for quantitative, single-cell, and subcellular characterization of multiple analytes in formalin-fixed paraffin-embedded tissue. Chemical inactivation of fluorescent dyes after each image acquisition round allows reuse of common dyes in iterative staining and imaging cycles. The mild inactivation chemistry is compatible with total and phosphoprotein detection, as well as DNA FISH. Accurate computational registration of sequential images is achieved by aligning nuclear counterstain-derived fiducial points. Individual cells, plasma membrane, cytoplasm, nucleus, tumor, and stromal regions are segmented to achieve cellular and subcellular quantification of multiplexed targets. In a comparison of pathologist scoring of diaminobenzidine staining of serial sections and automated MxIF scoring of a single section, human epidermal growth factor receptor 2, estrogen receptor, p53, and androgen receptor staining by diaminobenzidine and MxIF methods yielded similar results. Single-cell staining patterns of 61 protein antigens by MxIF in 747 colorectal cancer subjects reveals extensive tumor heterogeneity, and cluster analysis of divergent signaling through ERK1/2, S6 kinase 1, and 4E binding protein 1 provides insights into the spatial organization of mechanistic target of rapamycin and MAPK signal transduction. Our results suggest MxIF should be broadly applicable to problems in the fields of basic biological research, drug discovery and development, and clinical diagnostics. PMID:23818604

Highly multiplexed single-cell analysis of formalin-fixed, paraffin-embedded cancer tissue.

PubMed

Gerdes, Michael J; Sevinsky, Christopher J; Sood, Anup; Adak, Sudeshna; Bello, Musodiq O; Bordwell, Alexander; Can, Ali; Corwin, Alex; Dinn, Sean; Filkins, Robert J; Hollman, Denise; Kamath, Vidya; Kaanumalle, Sireesha; Kenny, Kevin; Larsen, Melinda; Lazare, Michael; Li, Qing; Lowes, Christina; McCulloch, Colin C; McDonough, Elizabeth; Montalto, Michael C; Pang, Zhengyu; Rittscher, Jens; Santamaria-Pang, Alberto; Sarachan, Brion D; Seel, Maximilian L; Seppo, Antti; Shaikh, Kashan; Sui, Yunxia; Zhang, Jingyu; Ginty, Fiona

2013-07-16

Limitations on the number of unique protein and DNA molecules that can be characterized microscopically in a single tissue specimen impede advances in understanding the biological basis of health and disease. Here we present a multiplexed fluorescence microscopy method (MxIF) for quantitative, single-cell, and subcellular characterization of multiple analytes in formalin-fixed paraffin-embedded tissue. Chemical inactivation of fluorescent dyes after each image acquisition round allows reuse of common dyes in iterative staining and imaging cycles. The mild inactivation chemistry is compatible with total and phosphoprotein detection, as well as DNA FISH. Accurate computational registration of sequential images is achieved by aligning nuclear counterstain-derived fiducial points. Individual cells, plasma membrane, cytoplasm, nucleus, tumor, and stromal regions are segmented to achieve cellular and subcellular quantification of multiplexed targets. In a comparison of pathologist scoring of diaminobenzidine staining of serial sections and automated MxIF scoring of a single section, human epidermal growth factor receptor 2, estrogen receptor, p53, and androgen receptor staining by diaminobenzidine and MxIF methods yielded similar results. Single-cell staining patterns of 61 protein antigens by MxIF in 747 colorectal cancer subjects reveals extensive tumor heterogeneity, and cluster analysis of divergent signaling through ERK1/2, S6 kinase 1, and 4E binding protein 1 provides insights into the spatial organization of mechanistic target of rapamycin and MAPK signal transduction. Our results suggest MxIF should be broadly applicable to problems in the fields of basic biological research, drug discovery and development, and clinical diagnostics.

Self-Assembled ZnO Nanosheet-Based Spherical Structure as Photoanode in Dye-Sensitized Solar Cells

NASA Astrophysics Data System (ADS)

Ameri, Mohsen; Raoufi, Meysam; Zamani-Meymian, M.-R.; Samavat, Feridoun; Fathollahi, M.-R.; Mohajerani, Ezeddin

2018-03-01

High surface area and enhanced light scattering of ZnO nanosheet aggregates have made them a promising active layer candidate material for fabrication of nanostructure dye-sensitized solar cells. Here, we propose a facile preparation method of such ZnO nanosheet structures, and in order to verify their applicability as photoanode material for dye-sensitized solar cells, we employ morphological, optical, structural and electrical measurements. The results reveal the high surface area available for dye molecules for enhancing adsorption, high light scattering and competitive power conversion efficiencies compared to the works in literature. Finally, the device is optimized with respect to the photoanode thickness. The favorable features shown here can extend the application of the structure to other types of sensitization-based perovskite and quantum dot solar cells.

Mesoporous aluminosilicate glasses: Potential materials for dye removal from wastewater effluents

NASA Astrophysics Data System (ADS)

Almeida, Flavio P.; Botelho, Moema B. S.; Doerenkamp, Carsten; Kessler, Elizaveta; Ferrari, Cynthia R.; Eckert, Hellmut; de Camargo, Andrea S. S.

2017-09-01

Mesoporous amorphous sodium-aluminosilicate host matrices of composition Si1-xAlxNaxO2, 0.1 ≤ x ≤ 0.33, obtained by sol-gel methodology, have been used as sequestrating agents for the cationic dye Rhodamine 6 G (Rh6G) in solution. Favorable adsorption kinetics and a wide pH working range (4-10) as well as high sorption capacities for Rh6G render these materials potentially useful reagents for effective dye removal from wastewaters. While the experimentally realized sorption capacities fall significantly below the theoretical limits, used materials can be thermally re-cycled by pyrolizing the sequestrated dye molecules. Solid state NMR and BET measurements show that this process occurs under preservation of the materials' structural integrity, allowing it to be re-used multiple times.

Study of chemical reactivity in relation to experimental parameters of efficiency in coumarin derivatives for dye sensitized solar cells using DFT.

PubMed

Soto-Rojo, Rody; Baldenebro-López, Jesús; Glossman-Mitnik, Daniel

2015-06-07

A group of dyes derived from coumarin was studied, which consisted of nine molecules using a very similar manufacturing process of dye sensitized solar cells (DSSCs). Optimized geometries, energy levels of the highest occupied molecular orbital and the lowest unoccupied molecular orbital, and ultraviolet-visible spectra were obtained using theoretical calculations, and they were also compared with experimental conversion efficiencies of the DSSC. The representation of an excited state in terms of natural transition orbitals (NTOs) was studied. Chemical reactivity parameters were calculated and correlated with the experimental data linked to the efficiency of the DSSC. A new proposal was obtained to design new molecular systems and to predict their potential use as a dye in DSSCs.

Topographically induced homeotropic alignment of liquid crystals on self-assembled opal crystals.

PubMed

Kumar, Pankaj; Oh, Su Yeon; Baliyan, Vijay K; Kundu, Sudarshan; Lee, Seung Hee; Kang, Shin-Woong

2018-04-02

The surface of multilayered opal crystals resulted in homeotropic alignment of liquid crystal (LC), originated from the surface topography of opal crystals rather than a chemical nature of the nanoparticles. The polar anchoring energy (5.51 × 10 -5 J/m 2 ) of the crystal surface for nematic LC molecules was in a similar range to the conventional polyimide alignment layer (2.11 × 10 -5 J/m 2 ) used for commercial applications. The critical length scale for anchoring transition was approximately Lw = ~1 μm. If a diameter of particle d < 1 μm for opal crystals, LC molecules preferred to anchor vertically to the surface to minimize elastic free energy of bulk LCs. The LC favored a planar anchoring if d > 1 μm. The results provide crucial insights to understand the homeotropic alignment of LCs on solid surfaces and therefore offer opportunities to develop novel materials for a vertical alignment of LCs.

Regenerable Photovoltaic Devices with a Hydrogel-Embedded Microvascular Network

PubMed Central

Koo, Hyung-Jun; Velev, Orlin D.

2013-01-01

Light-driven degradation of photoactive molecules could be one of the major obstacles to stable long term operation of organic dye-based solar light harvesting devices. One solution to this problem may be mimicking the regeneration functionality of a plant leaf. We report an organic dye photovoltaic system that has been endowed with such microfluidic regeneration functionality. A hydrogel medium with embedded channels allows rapid and uniform supply of photoactive reagents by a convection-diffusion mechanism. A washing-activation cycle enables reliable replacement of the organic component in a dye-sensitized photovoltaic system. Repetitive restoration of photovoltaic performance after intensive device degradation is demonstrated. PMID:23912814

Long-term luminescence of sensibilizers in tissues at the conditions of oxygen deficiency due to photodynamic effect

NASA Astrophysics Data System (ADS)

Ishemgulov, A. T.; Letuta, S. N.; Pashkevich, S. N.; Alidzhanov, E. K.; Lantukh, Yu. D.

2017-11-01

Long-term luminescence of organic dyes (xanthene dyes, halogen substituted fluoroscein) was used for an in vitro study of the photodynamic effect of exogenic probes in malignant tumors and healthy tissues of mice. It is shown that the photodynamic activity of oxygen and the dynamics of its concentration in tissues can be estimated from the delayed fluorescence of exogenic probes caused by singlet-triplet annihilation of singlet oxygen and excited triplet states of the molecules of photosensitizer dyes. It is found that quenching of long-term luminescence of photosensitizers significantly differs in tumors and normal tissues.

A New Class of Stable Heptamethine Cyanine Fluorophores and Biomedical Applications Thereof | NCI Technology Transfer Center | TTC

Cancer.gov

Researchers at the National Cancer Institute (NCI) have developed an improved class of heptamethine cyanine fluorophore dyes useful for imaging applications in the near-IR range (750-850 nm). A new chemical reaction has been developed that provides easy access to novel molecules with improved properties. Specifically, the dyes display greater resistance to thiol nucleophiles, and are more robust while maintaining excellent optical properties. The dyes have been successfully employed in various in vivo imaging applications and in vitro labeling and microscopy applications. The NCI seek co-development or licensees to develop them as targetable agents for optical-guided surgical interventions.

Gold nanoparticle-based plasmonic random fiber laser

NASA Astrophysics Data System (ADS)

Hu, Zhijia; Liang, Yunyun; Xie, Kang; Gao, Pengfei; Zhang, Douguo; Jiang, Haiming; Shi, Fan; Yin, Leicheng; Gao, Jiangang; Ming, Hai; Zhang, Qijin

2015-03-01

We have reported the realization of a plasmonic random fiber laser based on the localized surface plasmonic resonance of gold nanoparticles (NPs) in the liquid core optical fiber. The liquid core material contains a dispersive solution of gold NPs and laser dye pyrromethene 597 in toluene. It was experimentally proved that the fluorescence quenching of the dye is restrained in the optical fiber, which is considered one of the main sources of loss in the traditional laser system. Meanwhile, the random lasing can be more easily obtained in the random laser system with more overlap between the plasmonic resonance of the gold NPs and the photoluminescence spectrum of the dye molecules.

Electrostrictive Graft Elastomers

NASA Technical Reports Server (NTRS)

Su, Ji (Inventor); Harrison, Joycelyn S. (Inventor); St.Clair, Terry L. (Inventor)

2003-01-01

An electrostrictive graft elastomer has a backbone molecule which is a non-crystallizable, flexible macromolecular chain and a grafted polymer forming polar graft moieties with backbone molecules. The polar graft moieties have been rotated by an applied electric field, e.g., into substantial polar alignment. The rotation is sustained until the electric field is removed. In another embodiment, a process for producing strain in an elastomer includes: (a) providing a graft elastomer having a backbone molecule which is a non-crystallizable, flexible macromolecular chain and a grafted polymer forming polar graft moieties with backbone molecules; and (b) applying an electric field to the graft elastomer to rotate the polar graft moieties, e.g., into substantial polar alignment.

Organic-inorganic nanostructures for luminescent indication in the near-infrared range

NASA Astrophysics Data System (ADS)

Kondratenko, T. S.; Ovchinnikov, O. V.; Grevtseva, I. G.; Smirnov, M. S.

2016-04-01

Amplifying and quenching of IR luminescence of colloidal Ag2S quantum dots were revealed to take place when they couple to organic dye molecules of 3,3'-di-(γ-sulfopropyl)-9-ethyl-4,5,4',5'-dibenzothiacarbocyanine betaine and erytrosine pyridinium salts, respectively. The observed effects are explained as due to the formation of organic-inorganic heterostructures with different mutual arrangement of electronic states of the dyes and the quantum dots.

Mild extraction methods using aqueous glucose solution for the analysis of natural dyes in textile artefacts dyed with Dyer's madder (Rubia tinctorum L.).

PubMed

Ford, Lauren; Henderson, Robert L; Rayner, Christopher M; Blackburn, Richard S

2017-03-03

Madder (Rubia tinctorum L.) has been widely used as a red dye throughout history. Acid-sensitive colorants present in madder, such as glycosides (lucidin primeveroside, ruberythric acid, galiosin) and sensitive aglycons (lucidin), are degraded in the textile back extraction process; in previous literature these sensitive molecules are either absent or present in only low concentrations due to the use of acid in typical textile back extraction processes. Anthraquinone aglycons alizarin and purpurin are usually identified in analysis following harsh back extraction methods, such those using solvent mixtures with concentrated hydrochloric acid at high temperatures. Use of softer extraction techniques potentially allows for dye components present in madder to be extracted without degradation, which can potentially provide more information about the original dye profile, which varies significantly between madder varieties, species and dyeing technique. Herein, a softer extraction method involving aqueous glucose solution was developed and compared to other back extraction techniques on wool dyed with root extract from different varieties of Rubia tinctorum. Efficiencies of the extraction methods were analysed by HPLC coupled with diode array detection. Acidic literature methods were evaluated and they generally caused hydrolysis and degradation of the dye components, with alizarin, lucidin, and purpurin being the main compounds extracted. In contrast, extraction in aqueous glucose solution provides a highly effective method for extraction of madder dyed wool and is shown to efficiently extract lucidin primeveroside and ruberythric acid without causing hydrolysis and also extract aglycons that are present due to hydrolysis during processing of the plant material. Glucose solution is a favourable extraction medium due to its ability to form extensive hydrogen bonding with glycosides present in madder, and displace them from the fibre. This new glucose method offers an efficient process that preserves these sensitive molecules and is a step-change in analysis of madder dyed textiles as it can provide further information about historical dye preparation and dyeing processes that current methods cannot. The method also efficiently extracts glycosides in artificially aged samples, making it applicable for museum textile artefacts. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Monitoring Integrated Activity of Individual Neurons Using FRET-Based Voltage-Sensitive Dyes.

PubMed

Briggman, Kevin L; Kristan, William B; González, Jesús E; Kleinfeld, David; Tsien, Roger Y

2015-01-01

Pairs of membrane-associated molecules exhibiting fluorescence resonance energy transfer (FRET) provide a sensitive technique to measure changes in a cell's membrane potential. One of the FRET pair binds to one surface of the membrane and the other is a mobile ion that dissolves in the lipid bilayer. The voltage-related signal can be measured as a change in the fluorescence of either the donor or acceptor molecules, but measuring their ratio provides the largest and most noise-free signal. This technology has been used in a variety of ways; three are documented in this chapter: (1) high throughput drug screening, (2) monitoring the activity of many neurons simultaneously during a behavior, and (3) finding synaptic targets of a stimulated neuron. In addition, we provide protocols for using the dyes on both cultured neurons and leech ganglia. We also give an updated description of the mathematical basis for measuring the coherence between electrical and optical signals. Future improvements of this technique include faster and more sensitive dyes that bleach more slowly, and the expression of one of the FRET pair genetically.

Thermal bleaching in single fluorescent molecules under two-photon excitation regime

NASA Astrophysics Data System (ADS)

Chirico, Giuseppe; Cannone, Fabio; Baldini, Giancarlo; Diaspro, Alberto

2003-07-01

Single molecule spectroscopy often requires the immobilization of the molecules onto solid or quasi-solid substrates and the use of relatively high excitation intensity We have studied the fluorescence emission of four common dyes used for bio-imaging studies, rhodamine 6G, fluorescein, pyrene and indo-1 at the single molecule level under two-photon excitation regime. We focus on two-photon excitation thermal effects on the stability of the single molecules, influencing the internal photo-dynamics and the total duration of the fluorescent emission. Single dye molecules, spread on a glass substrate by spin coating, show a constant fluorescence output till a sudden transition to a dark state very close to the background. The bleaching time that is found to vary in the series pyrene, Indo-1, fluorescein and rhodamine 6G from the fastest to the slowest one respectively, has a Gaussian distribution suggesting that bleaching is not due to photo-bleaching. Moreover it shows a correlation to the amount of absorbed power not re-irradiated as fluorescence and to the complexity of the molecule. These observations are interpreted as thermal bleaching where the temperature increase is induced by the two-photon excitation process. This study should be extended to different trapping media of interest in single molecule basic research and applications, such as silica and polyacrylamide gels or nanosctructured polyelectrolyte matrices. We think that the observed behavior and the correlations found to the molecular chemical and physical parameters, may be of some help for the design of molecules with switching on-off behavior of longer duration.

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.

Polymer based plasmonic elements with dye molecules

NASA Astrophysics Data System (ADS)

Zhang, Douguo; Wang, Xiangxian; Chen, Yikai; Han, Lu; Wang, Pei; Ming, Hai

2012-11-01

Recently, dielectric loaded surface plasmons (SPs) elements are inducing highly interesting in the field of nanooptics, which are composed of dielectric nanostructures fabricated on a metallic thin film. This configuration will provide a route to novel integrated micro-optical devices and components combining photonics and electronics on the same chip. The advantages are easy fabrication, easy integration, and also the potential to realizing active plasmonic devices. In this talk, we will present our recent work in this field. Polymer (PMMA) nano-structures are fabricated on a silver film by the electron beam lithography (EBL) and laser interference lithography. These nano-structures are used to manipulate the behaviors of the SPs, such as converging, diverging, and guiding the propagation of SPs in subwavelength scale. Except for the pure PMMA nano-structures, dye materials (Rhodamine B, RhB) doped PMMA structures are also fabricated on the silver film. The RhB molecules will work as the active medium to excite the SPs or compensation the loss of SPs wave. The dye doped PMMA nanostructure provides a choice to realize active plasmonic elements, such as SPs Bragg gratings. On the other hand, the interaction between the fluorescence molecules and SPs will give rise to some new optical phenomena, such as directional fluorescence emission, anisotropic fluorescence emission. These polymer based plasmonic structures are investigated with a home-built leakage radiation microscopy (LRM).

Role of surfactant derived intermediates in the efficacy and mechanism for radiation chemical degradation of a hydrophobic azo dye, 1-phenylazo-2-naphthol.

PubMed

Das, Laboni; Chatterjee, Suchandra; Naik, Devidas B; Adhikari, Soumyakanti

2015-11-15

A combined methodology involving gamma and pulse radiolysis, product analysis and toxicity studies has been adopted to comprehend the degradation process of a model hydrophobic azo dye, 1-phenylazo-2-naphthol, emphasizing the role of the surfactant, which is an integral part of textile waste. Two new and important findings are underlined in this article. The first is the direct attestation of the hydrazyl radical-parent adduct, formed in the reaction of the dye with e(-)aq followed by protonation and subsequent addition to the unreacted dye molecule. This has been confirmed from concentration dependent studies. Secondly, we have clearly shown that in the reaction of hydroxyl radical with the dye in Triton X-100 media, the initially produced TX radicals cause reductive degradation of the dye. Identification and detailed analysis of HPLC and GCMS data reveals that similar products are formed in both the reactions of e(-)aq and OH radicals. Moreover, the cytotoxicity of 10(-4)moldm(-3) dye was found to be reduced significantly after irradiation. Thus, the present study not only depicts new pathways for the degradation of hydrophobic azo dye, but also demonstrates the role of a surfactant in the entire process. Copyright © 2015 Elsevier B.V. All rights reserved.

Assessment of Free Dye in Solutions of Dual-Labeled Antibody Conjugates for In Vivo Molecular Imaging

PubMed Central

Aldrich, Melissa B.; Wang, XueJuan; Hart, Amy; Sampath, Lakshmi; Marshall, Milton V.; Sevick-Muraca, Eva M.

2017-01-01

PURPOSE Recent preclinical and clinical studies show dyes that excite and fluoresce in the near infrared range may be used for tracking and detecting disease targets in vivo. A method for quantifying free dye molecules in antibody conjugate preparations is required for agent batch release and for translation into the clinic. PROCEDURES Herein, we developed and validated a SDS-PAGE method to determine the percentage of free IRDye 800CW in (DTPA)n-trastuzumab—(IRDye 800)m conjugate sample preparations in which HPLC assessment of free dye was not possible. RESULTS The SDS-PAGE assay was accurate and valid for free IRDye 800CW amounts between 38 and 4 molar percent of total dye. Gel sample preparation reagent affected the specificity of the assay, and lower and upper limits of quantitation and detection were determined. CONCLUSION This method may be applicable to other near infrared dye-conjugated antibody-based imaging agents in which HPLC assessment of purity is not feasible. This validated method for quality assurance will facilitate the translation of dual-labeled antibody conjugates for nuclear and optical imaging. PMID:20458634

Rational molecular engineering of cyclopentadithiophene-bridged D-A-π-A sensitizers combining high photovoltaic efficiency with rapid dye adsorption

PubMed Central

Chai, Qipeng; Li, Wenqin; Liu, Jingchuan; Geng, Zhiyuan; Tian, He; Zhu, Wei-hong

2015-01-01

Dye-sensitized solar cell (DSSC) is considered as a feasible route to the clean and renewable energy conversion technique. The commercial application requires further enhancements on photovoltaic efficiency and simplification on the device fabrication. For avoiding the unpreferable trade-off between photocurrent (JSC) and photovoltage (VOC), here we report the molecular engineering and comprehensive photovoltaic characterization of three cyclopentadithiophene-bridged D-A-π-A motif sensitizers with a change in donor group. We make a careful choice on the donor and conjugation bridge for synergistically increasing JSC and VOC. Comparing with the reference dye WS-2, the photovoltaic efficiency with the single component dye of WS-51 increases by 18%, among one of the rare examples in pure metal-free organic dyes exceeding 10% in combination with traditional iodine redox couples. Moreover, WS-51 exhibits several prominent merits on potentially scale-up industrial application: i) facile synthetic route to target molecule, ii) simple dipping procedure without requirement of co-sensitization, and iii) rapid dye adsorption capability. PMID:26066974

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.

FLASHFLOOD: A 3D Field-based similarity search and alignment method for flexible molecules

NASA Astrophysics Data System (ADS)

Pitman, Michael C.; Huber, Wolfgang K.; Horn, Hans; Krämer, Andreas; Rice, Julia E.; Swope, William C.

2001-07-01

A three-dimensional field-based similarity search and alignment method for flexible molecules is introduced. The conformational space of a flexible molecule is represented in terms of fragments and torsional angles of allowed conformations. A user-definable property field is used to compute features of fragment pairs. Features are generalizations of CoMMA descriptors (Silverman, B.D. and Platt, D.E., J. Med. Chem., 39 (1996) 2129.) that characterize local regions of the property field by its local moments. The features are invariant under coordinate system transformations. Features taken from a query molecule are used to form alignments with fragment pairs in the database. An assembly algorithm is then used to merge the fragment pairs into full structures, aligned to the query. Key to the method is the use of a context adaptive descriptor scaling procedure as the basis for similarity. This allows the user to tune the weights of the various feature components based on examples relevant to the particular context under investigation. The property fields may range from simple, phenomenological fields, to fields derived from quantum mechanical calculations. We apply the method to the dihydrofolate/methotrexate benchmark system, and show that when one injects relevant contextual information into the descriptor scaling procedure, better results are obtained more efficiently. We also show how the method works and include computer times for a query from a database that represents approximately 23 million conformers of seventeen flexible molecules.

Exonuclease III-Assisted Upconversion Resonance Energy Transfer in a Wash-Free Suspension DNA Assay.

PubMed

Chen, Yinghui; Duong, Hien T T; Wen, Shihui; Mi, Chao; Zhou, Yingzhu; Shimoni, Olga; Valenzuela, Stella M; Jin, Dayong

2018-01-02

Sensitivity is the key in optical detection of low-abundant analytes, such as circulating RNA or DNA. The enzyme Exonuclease III (Exo III) is a useful tool in this regard; its ability to recycle target DNA molecules results in markedly improved detection sensitivity. Lower limits of detection may be further achieved if the detection background of autofluorescence can be removed. Here we report an ultrasensitive and specific method to quantify trace amounts of DNA analytes in a wash-free suspension assay. In the presence of target DNA, the Exo III recycles the target DNA by selectively digesting the dye-tagged sequence-matched probe DNA strand only, so that the amount of free dye removed from the probe DNA is proportional to the number of target DNAs. Remaining intact probe DNAs are then bound onto upconversion nanoparticles (energy donor), which allows for upconversion luminescence resonance energy transfer (LRET) that can be used to quantify the difference between the free dye and tagged dye (energy acceptor). This scheme simply avoids both autofluorescence under infrared excitation and many tedious washing steps, as the free dye molecules are physically located away from the nanoparticle surface, and as such they remain "dark" in suspension. Compared to alternative approaches requiring enzyme-assisted amplification on the nanoparticle surface, introduction of probe DNAs onto nanoparticles only after DNA hybridization and signal amplification steps effectively avoids steric hindrance. Via this approach, we have achieved a detection limit of 15 pM in LRET assays of human immunodeficiency viral DNA.

Discoloration and detoxicification of a Congo red dye solution by means of ozone treatment for a possible water reuse.

PubMed

Khadhraoui, M; Trabelsi, H; Ksibi, M; Bouguerra, S; Elleuch, B

2009-01-30

The objective of this study was to investigate the degradation and mineralization of an azo-dye, the Congo red, in aqueous solutions using ozone. Phytotoxicity and the inhibitory effects on the microbial activity of the raw and the ozonated solutions were also carried out with the aim of water reuse and environment protection. Decolorization of the aqueous solutions, disappearance of the parent compound, chemical oxygen demand (COD) and total organic carbon (TOC) removal were the main parameters monitored in this study. To control the mineralization of the Congo red, pH of the ozonated solution and heteroatoms released from the mother molecule such NH(4)(+), NO(3)(-) and SO(4)(2-) were determined. It was concluded that ozone by itself is strong enough to decolorize these aqueous solutions in the early stage of the oxidation process. Nonetheless, efficient mineralization had not been achieved. Significant drops in COD (54%) were registered. The extent of TOC removal was about 32%. Sulfur heteroatom was totally oxidized to SO(4)(2-) ions while the central -NN- azo ring was partially converted to NH(4)(+) and NO(3)(-). Results of the kinetic studies showed that ozonation of the selected molecule was a pseudo-first-order reaction with respect to dye concentration. The obtained results also demonstrate that ozone process reduced the phytotoxicity of the raw solution and enhanced the biodegradability of the treated azo-dyes-wastewater. Hence, this show that ozone remains one of the effective technologies for the discoloration and the detoxification of organic dyes in wastewater.

The structure and protein binding of amyloid-specific dye reagents.

PubMed

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

2003-01-01

The self-assembling tendency and protein complexation capability of dyes related to Congo red and also some dyes of different structure were compared to explain the mechanism of Congo red binding and the reason for its specific affinity for beta-structure. Complexation with proteins was measured directly and expressed as the number of dye molecules bound to heat-aggregated IgG and to two light chains with different structural stability. Binding of dyes to rabbit antibodies was measured indirectly as the enhancement effect of the dye on immune complex formation. Self-assembling was tested using dynamic light scattering to measure the size of the supramolecular assemblies. In general the results show that the supramolecular form of a dye is the main factor determining its complexation capability. Dyes that in their compact supramolecular organization are ribbon-shaped may adhere to polypeptides of beta-conformation due to the architectural compatibility in this unique structural form. The optimal fit in complexation seems to depend on two contradictory factors involving, on the one hand, the compactness of the non-covalently stabilized supramolecular ligand, and the dynamic character producing its plasticity on the other. As a result, the highest protein binding capability is shown by dyes with a moderate self-assembling tendency, while those arranging into either very rigid or very unstable supramolecular entities are less able to bind.

A novel biosorbent for dye removal: extracellular polymeric substance (EPS) of Proteus mirabilis TJ-1.

PubMed

Zhang, Zhiqiang; Xia, Siqing; Wang, Xuejiang; Yang, Aming; Xu, Bin; Chen, Ling; Zhu, Zhiliang; Zhao, Jianfu; Jaffrezic-Renault, Nicole; Leonard, Didier

2009-04-15

This paper deals with the extracellular polymeric substance (EPS) of Proteus mirabilis TJ-1 used as a novel biosorbent to remove dye from aqueous solution in batch systems. As a widely used and hazardous dye, basic blue 54 (BB54) was chosen as the model dye to examine the adsorption performance of the EPS. The effects of pH, initial dye concentration, contact time and temperature on the sorption of BB54 to the EPS were examined. At various initial dye concentrations (50-400 mg/L), the batch sorption equilibrium can be obtained in only 5 min. Kinetic studies suggested that the sorption followed the internal transport mechanism. According to the Langmuir model, the maximum BB54 uptake of 2.005 g/g was obtained. Chemical analysis of the EPS indicated the presence of protein (30.9%, w/w) and acid polysaccharide (63.1%, w/w). Scanning electron microscopy (SEM) images showed that the EPS with a crystal-linear structure was whole enwrapped by adsorbed dye molecules. FTIR spectrum result revealed the presence of adsorbing groups such as carboxyl, hydroxyl and amino groups in the EPS. High-molecular weight of the EPS with more binding-sites and stronger van der Waals forces together with its specific construct leads to the excellent performance of dye adsorption. The EPS shows potential board application as a biosorbent for both environmental protection and dye recovery.

The influence of local electric fields on photoinduced absorption in dye-sensitized solar cells.

PubMed

Cappel, Ute B; Feldt, Sandra M; Schöneboom, Jan; Hagfeldt, Anders; Boschloo, Gerrit

2010-07-07

The dye-sensitized solar cell (DSC) challenges conventional photovoltaics with its potential for low-cost production and its flexibility in terms of color and design. Transient absorption spectroscopy is widely used to unravel the working mechanism of DSCs. A surprising, unexplained feature observed in these studies is an apparent bleach of the ground-state absorption of the dye, under conditions where the dye is in the ground state. Here, we demonstrate that this feature can be attributed to a change of the local electric field affecting the absorption spectrum of the dye, an effect related to the Stark effect first reported in 1913. We present a method for measuring the effect of an externally applied electric field on the absorption of dye monolayers adsorbed on flat TiO(2) substrates. The measured signal has the shape of the first derivative of the absorption spectra of the dyes and reverses sign along with the reversion of the direction of the change in dipole moment upon excitation relative to the TiO(2) surface. A very similar signal is observed in photoinduced absorption spectra of dye-sensitized TiO(2) electrodes under solar cell conditions, demonstrating that the electric field across the dye molecules changes upon illumination. This result has important implications for the analysis of transient absorption spectra of DSCs and other molecular optoelectronic devices and challenges the interpretation of many previously published results.

Energy Level Alignment at the Interface between Linear-Structured Benzenediamine Molecules and Au(111) Surface

NASA Astrophysics Data System (ADS)

Li, Guo; Rangel, Tonatiuh; Liu, Zhenfei; Cooper, Valentino; Neaton, Jeffrey

Using density functional theory with model self-energy corrections, we calculate the adsorption energetics and geometry, and the energy level alignment of benzenediamine (BDA) molecules adsorbed on Au(111) surfaces. Our calculations show that linear structures of BDA, stabilized via hydrogen bonds between amine groups, are energetically more favorable than monomeric phases. Moreover, our self-energy-corrected calculations of energy level alignment show that the highest occupied molecular orbital energy of the BDA linear structure is deeper relative to the Fermi level relative to the isolated monomer and agrees well with the values measured with photoemission spectroscopy. This work supported by DOE.

Effects of electrostatic screening on the conformation of single DNA molecules confined in a nanochannel

NASA Astrophysics Data System (ADS)

Zhang, Ce; Zhang, Fang; van Kan, Jeroen A.; van der Maarel, Johan R. C.

2008-06-01

Single T4-DNA molecules were confined in rectangular-shaped channels with a depth of 300 nm and a width in the range of 150-300 nm casted in a poly(dimethylsiloxane) nanofluidic chip. The extensions of the DNA molecules were measured with fluorescence microscopy as a function of the ionic strength and composition of the buffer as well as the DNA intercalation level by the YOYO-1 dye. The data were interpreted with the scaling theory for a wormlike polymer in good solvent, including the effects of confinement, charge, and self-avoidance. It was found that the elongation of the DNA molecules with decreasing ionic strength can be interpreted in terms of an increase of the persistence length. Self-avoidance effects on the extension are moderate, due to the small correlation length imposed by the channel cross-sectional diameter. Intercalation of the dye results in an increase of the DNA contour length and a partial neutralization of the DNA charge, but besides effects of electrostatic origin it has no significant effect on the bare bending rigidity. In the presence of divalent cations, the DNA molecules were observed to contract, but they do not collapse into a condensed structure. It is proposed that this contraction results from a divalent counterion mediated attractive force between the segments of the DNA molecule.

Magnetic field effects in dye-sensitized solar cells controlled by different cell architecture.

PubMed

Klein, M; Pankiewicz, R; Zalas, M; Stampor, W

2016-07-21

The charge recombination and exciton dissociation are generally recognized as the basic electronic processes limiting the efficiency of photovoltaic devices. In this work, we propose a detailed mechanism of photocurrent generation in dye-sensitized solar cells (DSSCs) examined by magnetic field effect (MFE) technique. Here we demonstrate that the magnitude of the MFE on photocurrent in DSSCs can be controlled by the radius and spin coherence time of electron-hole (e-h) pairs which are experimentally modified by the photoanode morphology (TiO2 nanoparticles or nanotubes) and the electronic orbital structure of various dye molecules (ruthenium N719, dinuclear ruthenium B1 and fully organic squaraine SQ2 dyes). The observed MFE is attributed to magnetic-field-induced spin-mixing of (e-h) pairs according to the Δg mechanism.

Magnetic field effects in dye-sensitized solar cells controlled by different cell architecture

NASA Astrophysics Data System (ADS)

Klein, M.; Pankiewicz, R.; Zalas, M.; Stampor, W.

2016-07-01

The charge recombination and exciton dissociation are generally recognized as the basic electronic processes limiting the efficiency of photovoltaic devices. In this work, we propose a detailed mechanism of photocurrent generation in dye-sensitized solar cells (DSSCs) examined by magnetic field effect (MFE) technique. Here we demonstrate that the magnitude of the MFE on photocurrent in DSSCs can be controlled by the radius and spin coherence time of electron-hole (e-h) pairs which are experimentally modified by the photoanode morphology (TiO2 nanoparticles or nanotubes) and the electronic orbital structure of various dye molecules (ruthenium N719, dinuclear ruthenium B1 and fully organic squaraine SQ2 dyes). The observed MFE is attributed to magnetic-field-induced spin-mixing of (e-h) pairs according to the Δg mechanism.

Excitation laser energy dependence of surface-enhanced fluorescence showing plasmon-induced ultrafast electronic dynamics in dye molecules

NASA Astrophysics Data System (ADS)

Itoh, Tamitake; Yamamoto, Yuko S.; Tamaru, Hiroharu; Biju, Vasudevanpillai; Murase, Norio; Ozaki, Yukihiro

2013-06-01

We find unique properties accompanying surface-enhanced fluorescence (SEF) from dye molecules adsorbed on Ag nanoparticle aggregates, which generate surface-enhanced Raman scattering. The properties are observed in excitation laser energy dependence of SEF after excluding plasmonic spectral modulation in SEF. The unique properties are large blue shifts of fluorescence spectra, deviation of ratios between anti-Stokes SEF intensity and Stokes from those of normal fluorescence, super-broadening of Stokes spectra, and returning to original fluorescence by lower energy excitation. We elucidate that these properties are induced by electromagnetic enhancement of radiative decay rates exceeding the vibrational relaxation rates within an electronic excited state, which suggests that molecular electronic dynamics in strong plasmonic fields can be largely deviated from that in free space.

Electrospun nanofiber membranes for adsorption of dye molecules from textile wastewater

NASA Astrophysics Data System (ADS)

Akduman, C.; Akçakoca Kumbasar, E. P.; Morsunbul, S.

2017-10-01

The nanofiber membranes prepared by the electrospinning method have unique properties such as high specific surface area and high porosity with fine pores. These properties led electrospun nanofiber membranes to use for the removal of dye molecules from textile wastewater. In this study, a hydrophobic Thermoplastic Polyurethane (TPU) and a hydrophilic Poly (vinyl alcohol) (PVA) were selected for producing electrospun nanofibers and their sorption capacities were investigated. The largest sorption capacity reached to maximum 88.31 mg/g, belong to BTCA cross-linked PVA membranes due to hydrophilic character of PVA. Contrary to expectation, hydrophobic character of TPU was dominant and incorporation of CD to the TPU nanofibers did not affect the sorption of the TPU membranes, and showed very low adsorption capacity (14.48 mg/g).

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.

Linear dichroism of DNA: Characterization of the orientation distribution function caused by hydrodynamic shear

DOE PAGES

Sutherland, John C.

2017-04-15

Linear dichroism provides information on the orientation of chromophores part of, or bound to, an orientable molecule such as DNA. For molecular alignment induced by hydrodynamic shear, the principal axes orthogonal to the direction of alignment are not equivalent. Thus, the magnitude of the flow-induced change in absorption for light polarized parallel to the direction of flow can be more than a factor of two greater than the corresponding change for light polarized perpendicular to both that direction and the shear axis. The ratio of the two flow-induced changes in absorption, the dichroic increment ratio, is characterized using the orthogonalmore » orientation model, which assumes that each absorbing unit is aligned parallel to one of the principal axes of the apparatus. The absorption of the alienable molecules is characterized by components parallel and perpendicular to the orientable axis of the molecule. The dichroic increment ratio indicates that for the alignment of DNA in rectangular flow cells, average alignment is not uniaxial, but for higher shear, as produced in a Couette cell, it can be. The results from the simple model are identical to tensor models for typical experimental configuration. Approaches for measuring the dichroic increment ratio with modern dichrometers are further discussed.« less

Linear dichroism of DNA: Characterization of the orientation distribution function caused by hydrodynamic shear

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

Sutherland, John C.

Linear dichroism provides information on the orientation of chromophores part of, or bound to, an orientable molecule such as DNA. For molecular alignment induced by hydrodynamic shear, the principal axes orthogonal to the direction of alignment are not equivalent. Thus, the magnitude of the flow-induced change in absorption for light polarized parallel to the direction of flow can be more than a factor of two greater than the corresponding change for light polarized perpendicular to both that direction and the shear axis. The ratio of the two flow-induced changes in absorption, the dichroic increment ratio, is characterized using the orthogonalmore » orientation model, which assumes that each absorbing unit is aligned parallel to one of the principal axes of the apparatus. The absorption of the alienable molecules is characterized by components parallel and perpendicular to the orientable axis of the molecule. The dichroic increment ratio indicates that for the alignment of DNA in rectangular flow cells, average alignment is not uniaxial, but for higher shear, as produced in a Couette cell, it can be. The results from the simple model are identical to tensor models for typical experimental configuration. Approaches for measuring the dichroic increment ratio with modern dichrometers are further discussed.« less

Linear dichroism of DNA: Characterization of the orientation distribution function caused by hydrodynamic shear.

PubMed

Sutherland, John C

2017-04-15

Linear dichroism provides information on the orientation of chromophores part of, or bound to, an orientable molecule such as DNA. For molecular alignment induced by hydrodynamic shear, the principal axes orthogonal to the direction of alignment are not equivalent. Thus, the magnitude of the flow-induced change in absorption for light polarized parallel to the direction of flow can be more than a factor of two greater than the corresponding change for light polarized perpendicular to both that direction and the shear axis. The ratio of the two flow-induced changes in absorption, the dichroic increment ratio, is characterized using the orthogonal orientation model, which assumes that each absorbing unit is aligned parallel to one of the principal axes of the apparatus. The absorption of the alienable molecules is characterized by components parallel and perpendicular to the orientable axis of the molecule. The dichroic increment ratio indicates that for the alignment of DNA in rectangular flow cells, average alignment is not uniaxial, but for higher shear, as produced in a Couette cell, it can be. The results from the simple model are identical to tensor models for typical experimental configurations. Approaches for measuring the dichroic increment ratio with modern dichrometers are discussed. Copyright © 2017. Published by Elsevier Inc.

Optimization of processing parameters on the controlled growth of ZnO nanorod arrays for the performance improvement of solid-state dye-sensitized solar cells

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

Lee, Yi-Mu, E-mail: ymlee@nuu.edu.t; Yang, Hsi-Wen

2011-03-15

High-transparency and high quality ZnO nanorod arrays were grown on the ITO substrates by a two-step chemical bath deposition (CBD) method. The effects of processing parameters including reaction temperature (25-95 {sup o}C) and solution concentration (0.01-0.1 M) on the crystal growth, alignment, optical and electrical properties were systematically investigated. It has been found that these process parameters are critical for the growth, orientation and aspect ratio of the nanorod arrays, showing different structural and optical properties. Experimental results reveal that the hexagonal ZnO nanorod arrays prepared under reaction temperature of 95 {sup o}C and solution concentration of 0.03 M possessmore » highest aspect ratio of {approx}21, and show the well-aligned orientation and optimum optical properties. Moreover the ZnO nanorod arrays based heterojunction electrodes and the solid-state dye-sensitized solar cells (SS-DSSCs) were fabricated with an improved optoelectrical performance. -- Graphical abstract: The ZnO nanorod arrays demonstrate well-alignment, high aspect ratio (L/D{approx}21) and excellent optical transmittance by low-temperature chemical bath deposition (CBD). Display Omitted Research highlights: > Investigate the processing parameters of CBD on the growth of ZnO nanorod arrays. > Optimization of CBD process parameters: 0.03 M solution concentration and reaction temperature of 95 {sup o}C. > The prepared ZnO samples possess well-alignment and high aspect ratio (L/D{approx}21). > An n-ZnO/p-NiO heterojunction: great rectifying behavior and low leakage current. > SS-DSSC has J{sub SC} of 0.31 mA/cm{sup 2} and V{sub OC} of 590 mV, and an improved {eta} of 0.059%.« less

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.

Dye@bio-MOF-1 Composite as a Dual-Emitting Platform for Enhanced Detection of a Wide Range of Explosive Molecules.

PubMed

Wang, Chen; Tian, Li; Zhu, Wei; Wang, Shiqiang; Wang, Peng; Liang, Yun; Zhang, Wanlin; Zhao, Hongwei; Li, Guangtao

2017-06-14

By incorporating a cationic dye within a metal-organic framework (MOF) through an ion-exchange process, a responsive dye@bio-MOF-1 composite has been synthesized, serving as a dual-emitting platform for enhanced detection of different kinds of nitro-explosives, especially nitroalkanes, nitramines, and nitrate esters. The dye@bio-MOF-1 composite was constructed with free amines on their well-defined cavities, which is essential for the capture of explosives into their confined nanospace. It was observed that the encapsulation of explosives into the constructed dye@bio-MOF-1 composite could dramatically alter the luminescent properties of the dyes as well as the MOF skeletons owing to the size exclusivity and confinement-induced effect. For nitroaromatics, the dye@bio-MOF-1 composite exhibits turn-off responses via fluorescence quenching. Unexpectedly, the composite shows unique turn-on responses for aliphatic nitro-organics via confinement-induced enhancement, demonstrating enhanced ability to detecting different kinds of explosives selectively in aqueous solution. Furthermore, the dye@bio-MOF-1 film was facilely fabricated, making the chemical sensing more convenient and easier to realize the discrimination of the targeted explosives. The dual tunable responses indicate that dye@bio-MOF-1 composites are favorable materials for molecular sensing. On the basis of the host-guest properties of the constructed dye@bio-MOF-1 composite, our work can be further extended to sensing specific analytes with remarkable turn-on sensing properties, in particular those difficult to recognize with conventional methods.

Enzyme-mediated bacterial biodegradation of an azo dye (C.I. Acid blue 113): reuse of treated dye wastewater in post-tanning operations.

PubMed

Senthilvelan, T; Kanagaraj, J; Panda, R C

2014-11-01

"Dyeing" is a common practice used to color the hides during the post-tanning operations in leather processing generating plenty of wastewater. The waste stream containing dye as pollutant is severely harmful to living beings. An azo dye (C.I. Acid Blue 113) has been biodegraded effectively by bacterial culture mediated with azoreductase enzyme to reduce the pollution load in the present investigation. The maximum rate of dye degradation was found to be 96 ± 4 and 92 ± 4 % for the initial concentrations of 100 and 200 mg/l, respectively. The enzyme activity was measured using NADH as a substrate. Fourier transform infrared spectroscopy (FT-IR) analysis was confirmed that the transformation of azo linkage could be transformed into N2 or NH3 or incorporated into complete biomass. Breaking down of dye molecules to various metabolites (such as aniline, naphthalene-1,4-diamine, 3-aminobenzenesulfonic acid, naphthalene-1-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid, 5,8-diaminonaphthalene-1-sulfonic acid) was confirmed by gas chromatography and mass spectra (GC-MS) and mass (electrospray ionization (ESI)) spectra analysis. The treated wastewater could be reused for dyeing operation in the leather processing, and the properties of produced leather were evaluated by conventional methods that revealed to have improved dye penetration into the grain layer of experimental leather sample and resulted in high levelness of dyeing, which helps to obtain the desired smoothness and soft leather properties.

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.

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.

Structure determination of molecules in an alignment laser field by femtosecond photoelectron diffraction using an X-ray free-electron laser

PubMed Central

Minemoto, Shinichirou; Teramoto, Takahiro; Akagi, Hiroshi; Fujikawa, Takashi; Majima, Takuya; Nakajima, Kyo; Niki, Kaori; Owada, Shigeki; Sakai, Hirofumi; Togashi, Tadashi; Tono, Kensuke; Tsuru, Shota; Wada, Ken; Yabashi, Makina; Yoshida, Shintaro; Yagishita, Akira

2016-01-01

We have successfully determined the internuclear distance of I2 molecules in an alignment laser field by applying our molecular structure determination methodology to an I 2p X-ray photoelectron diffraction profile observed with femtosecond X-ray free electron laser pulses. Using this methodology, we have found that the internuclear distance of the sample I2 molecules in an alignment Nd:YAG laser field of 6 × 1011 W/cm2 is elongated by from 0.18 to 0.30 Å “in average” relatively to the equilibrium internuclear distance of 2.666 Å. Thus, the present experiment constitutes a critical step towards the goal of femtosecond imaging of chemical reactions and opens a new direction for the study of ultrafast chemical reaction in the gas phase. PMID:27934891

Optical determination of the electronic coupling and intercalation geometry of thiazole orange homodimer in DNA

NASA Astrophysics Data System (ADS)

Cunningham, Paul D.; Bricker, William P.; Díaz, Sebastián A.; Medintz, Igor L.; Bathe, Mark; Melinger, Joseph S.

2017-08-01

Sequence-selective bis-intercalating dyes exhibit large increases in fluorescence in the presence of specific DNA sequences. This property makes this class of fluorophore of particular importance to biosensing and super-resolution imaging. Here we report ultrafast transient anisotropy measurements of resonance energy transfer (RET) between thiazole orange (TO) molecules in a complex formed between the homodimer TOTO and double-stranded (ds) DNA. Biexponential homo-RET dynamics suggest two subpopulations within the ensemble: 80% intercalated and 20% non-intercalated. Based on the application of the transition density cube method to describe the electronic coupling and Monte Carlo simulations of the TOTO/dsDNA geometry, the dihedral angle between intercalated TO molecules is estimated to be 81° ± 5°, corresponding to a coupling strength of 45 ± 22 cm-1. Dye intercalation with this geometry is found to occur independently of the underlying DNA sequence, despite the known preference of TOTO for the nucleobase sequence CTAG. The non-intercalated subpopulation is inferred to have a mean inter-dye separation distance of 19 Å, corresponding to coupling strengths between 0 and 25 cm-1. This information is important to enable the rational design of energy transfer systems that utilize TOTO as a relay dye. The approach used here is generally applicable to determining the electronic coupling strength and intercalation configuration of other dimeric bis-intercalators.

The Kinetic Mechanism for DNA Unwinding by Multiple Molecules of Dda Helicase Aligned on DNA†

PubMed Central

Eoff, Robert L.; Raney, Kevin D.

2010-01-01

Helicases catalyze the separation of double-stranded nucleic acids to form single-stranded intermediates. Using transient state kinetic methods we have determined the kinetic properties of DNA unwinding under conditions that favor a monomeric form of the Dda helicase as well as conditions that allow multiple molecules to function on the same substrate. Multiple helicase molecules can align like a train on the DNA track. The number of base pairs unwound in a single binding event for Dda is increased from ~19 bp for the monomeric form to ~64 bp when as many as four Dda molecules are aligned on the same substrate, while the kinetic step-size (3.2 ± 0.7 bp) and unwinding rate (242 ± 25 bp s−1) appear to be independent of the number of Dda molecules present on a given substrate. The data support a model in which the helicase molecules bound to the same substrate move along the DNA track independently during DNA unwinding. The observed increase in processivity arises from the increased probability that at least one of the helicases will completely unwind the DNA prior to dissociation. These results are in contrast to previous reports in which multiple Dda molecules on the same track greatly enhanced the rate and amplitude for displacement of protein blocks on the track. Therefore, only when the progress of the lead molecule in the train is impeded by some type of block, such as a protein bound to DNA, do the trailing molecules interact with the lead molecule in order to overcome the block. The fact that trailing helicase molecules have little impact on the lead molecule in the train during routine DNA unwinding suggests that the trailing molecules are moving at similar rates as the lead molecule. This result implicates a step in the translocation mechanism as contributing greatly to the overall rate-limiting step for unwinding of duplex DNA. PMID:20408588

Apodizer aperture for lasers

DOEpatents

Jorna, Siebe; Siebert, Larry D.; Brueckner, Keith A.

1976-11-09

An aperture attenuator for use with high power lasers which includes glass windows shaped and assembled to form an annulus chamber which is filled with a dye solution. The annulus chamber is shaped such that the section in alignment with the axis of the incident beam follows a curve which is represented by the equation y = (r - r.sub.o).sup.n.

Everything you always wanted to know about black dye (but were afraid to ask): a DFT/TDDFT investigation.

PubMed

Fantacci, Simona; Lobello, Maria G; De Angelis, Filippo

2013-01-01

We report an exhaustive theoretical and computational investigation of the electronic, optical, redox and acid-base properties, along with the adsorption mode on TiO2, of Black Dye (BD), the prototypical panchromatic dye for solar cell applications. We investigated in detail the variation of the relevant dye properties as a function of the solution pH, corresponding to the stepwise deprotonation of the carboxylic groups. Our results reproduced the expected blue-shift of the optical absorption spectrum and the experimental trend of oxidation potentials by increasing pH, which turned both out to be in excellent agreement with experimental values. Also, our calculated excited state oxidation potential is in good agreement with available experimental data. We then looked at the pKa of the various deprotonation steps, finding lowest pKa values for the stepwise dissociation of three protons of 2.71, 3.69 and 5.20, in excellent agreement with experimental pKa values of 3 and 5, for two and one protons dissociation, respectively. We finally investigated the adsorption of BD on TiO2, finding the most stable adsorption to occur via two dissociated monodentate carboxylic groups. Inspection of the electronic structure and alignment of energy levels for N719 and BD revealed a reduced driving force for electron injection in the latter dye, which could possibly lead to energetically unfavorable electron transfer from the excited dye to the TiO2 conduction band. Our results may constitute a reference study for future investigations and optimization of BD-based dye-sensitized solar cells.

Electrically tunable laser based on oblique heliconical cholesteric liquid crystal

PubMed Central

Xiang, Jie; Varanytsia, Andrii; Minkowski, Fred; Paterson, Daniel A.; Storey, John M. D.; Imrie, Corrie T.; Lavrentovich, Oleg D.; Palffy-Muhoray, Peter

2016-01-01

A cholesteric liquid crystal (CLC) formed by chiral molecules represents a self-assembled one-dimensionally periodic helical structure with pitch p in the submicrometer and micrometer range. Because of the spatial periodicity of the dielectric permittivity, a CLC doped with a fluorescent dye and pumped optically is capable of mirrorless lasing. An attractive feature of a CLC laser is that the pitch p and thus the wavelength of lasing λ¯ can be tuned, for example, by chemical composition. However, the most desired mode to tune the laser, by an electric field, has so far been elusive. Here we present the realization of an electrically tunable laser with λ¯ spanning an extraordinarily broad range (>100 nm) of the visible spectrum. The effect is achieved by using an electric-field-induced oblique helicoidal (OH) state in which the molecules form an acute angle with the helicoidal axis rather than align perpendicularly to it as in a field-free CLC. The principal advantage of the electrically controlled CLCOH laser is that the electric field is applied parallel to the helical axis and thus changes the pitch but preserves the single-harmonic structure. The preserved single-harmonic structure ensures efficiency of lasing in the entire tunable range of emission. The broad tuning range of CLCOH lasers, coupled with their microscopic size and narrow line widths, may enable new applications in areas such as diagnostics, sensing, microscopy, displays, and holography. PMID:27807135

Electrically tunable laser based on oblique heliconical cholesteric liquid crystal.

PubMed

Xiang, Jie; Varanytsia, Andrii; Minkowski, Fred; Paterson, Daniel A; Storey, John M D; Imrie, Corrie T; Lavrentovich, Oleg D; Palffy-Muhoray, Peter

2016-11-15

A cholesteric liquid crystal (CLC) formed by chiral molecules represents a self-assembled one-dimensionally periodic helical structure with pitch [Formula: see text] in the submicrometer and micrometer range. Because of the spatial periodicity of the dielectric permittivity, a CLC doped with a fluorescent dye and pumped optically is capable of mirrorless lasing. An attractive feature of a CLC laser is that the pitch [Formula: see text] and thus the wavelength of lasing [Formula: see text] can be tuned, for example, by chemical composition. However, the most desired mode to tune the laser, by an electric field, has so far been elusive. Here we present the realization of an electrically tunable laser with [Formula: see text] spanning an extraordinarily broad range (>100 nm) of the visible spectrum. The effect is achieved by using an electric-field-induced oblique helicoidal (OH) state in which the molecules form an acute angle with the helicoidal axis rather than align perpendicularly to it as in a field-free CLC. The principal advantage of the electrically controlled CLC OH laser is that the electric field is applied parallel to the helical axis and thus changes the pitch but preserves the single-harmonic structure. The preserved single-harmonic structure ensures efficiency of lasing in the entire tunable range of emission. The broad tuning range of CLC OH lasers, coupled with their microscopic size and narrow line widths, may enable new applications in areas such as diagnostics, sensing, microscopy, displays, and holography.

Elution of Labile Fluorescent Dye from Nanoparticles during Biological Use

PubMed Central

Tenuta, Tiziana; Monopoli, Marco P.; Kim, JongAh; Salvati, Anna; Dawson, Kenneth A.; Sandin, Peter; Lynch, Iseult

2011-01-01

Cells act as extremely efficient filters for elution of unbound fluorescent tags or impurities associated with nanoparticles, including those that cannot be removed by extensive cleaning. This has consequences for quantification of nanoparticle uptake and sub-cellular localization in vitro and in vivo as a result of the presence of significant amount of labile dye even following extensive cleaning by dialysis. Polyacrylamide gel electrophoresis (PAGE) can be used to monitor the elution of unbound fluorescent probes from nanoparticles, either commercially available or synthesized in-house, and to ensure their complete purification for biological studies, including cellular uptake and sub-cellular localisation. Very different fluorescence distribution within cells is observed after short dialysis times versus following extensive dialysis against a solvent in which the free dye is more soluble, due to the contribution from free dye. In the absence of an understanding of the presence of residual free dye in (most) labeled nanoparticle solutions, the total fluorescence intensity in cells following exposure to nanoparticle solutions could be mis-ascribed to the presence of nanoparticles through the cell, rather than correctly assigned to either a combination of free-dye and nanoparticle-bound dye, or even entirely to free dye depending on the exposure conditions (i.e. aggregation of the particles etc). Where all of the dye is nanoparticle-bound, the particles are highly localized in sub-cellular organelles, likely lysosomes, whereas in a system containing significant amounts of free dye, the fluorescence is distributed through the cell due to the free diffusion of the molecule dye across all cellular barriers and into the cytoplasm. PMID:21998668

Optimizing Ionic Electrolytes for Dye-Sensitized Solar Cells

NASA Astrophysics Data System (ADS)

Fan, Xiaojuan; Hall, Sarah

2009-03-01

Dye-sensitized solar cells DSSCs provide next generation, low cost, and easy fabrication photovoltaic devices based on organic sensitizing molecules, polymer gel electrolyte, and metal oxide semiconductors. One of the key components is the solvent-free ionic liquid electrolyte that has low volatility and high stability. We report a rapid and low cost method to fabricate ionic polymer electrolyte used in DSSCs. Poly(ethylene oxide) (PEO) is blended with imidazolinium salt without any chemical solvent to form a gel electrolyte. Uniform and crack-free porous TiO2 thin films are sensitized by porphrine dye covered by the synthesized gel electrolyte. The fabricated DSSCs are more stable and potentially increase the photo-electricity conversion efficiency.

Application of LIF technique for the space- and time-resolved monitoring of pollutant gas decomposition in nonthermal plasma reactors

NASA Astrophysics Data System (ADS)

Mizeraczyk, Jerzy; Ohkubo, Toshikazu; Kanazawa, Seiji; Kocik, Marek

2003-10-01

Laser-induced fluorescence (LIF) technique aided by intensified CCD light signal detection and fast digital image processing is demonstrated to be a useful diagnostic method for in-situ observation of the discharge-induced plasma-chemistry processes responsible for NOx(NO + NO2) decomposition occurring in non-thermal plasma reactors. In this paper a method and results of the LIF measurement of two-dimensional distribution of the ground-state NO molecule density inside a DC positive streamer corona reactor during NO removal from a flue gas simulator [air/NO(up to 300 ppm)] are presented. Either a needle-to-plate or nozzle-to-plate electrode system, having an electrode gap of 30-50 mm was used for generating the corona discharge in the reactor. The LIF monitoring of NO molecules was carried out under the steady-state DC corona discharge condition. The laser-induced fluorescence on the transition NO X2Π(v"=0)<--A2Σ+(v'=0) at λ=226nm was chosen for monitoring ground-state NO molecules in the reactor. This transition was induced by irradiation of the NO molecules with UV laser pulses generated by a laser system consisted of a XeF excimer laser, dye laser and BBO crystal. The laser pulses from the XeF excimer laser (Lambda Physik, Complex 150, λ=351 nm) pumped the dye laser (Lambda Physik, Scanmate) with Coumarin 47 as a dye, which generated the laser beam of a wavelength turned around λ=450 nm. Then, the tuned dye laser beam pumped the BBO crystal in which the second harmonic radiation of a wavelength correspondingly tuned around λ=226 nm was generated. The 226-nm UV laser pulses of energy of 0.8-2 mJ and duration of about 20 ns were transformed into the form of the so-called laser sheet (width of 1 mm, height of 30-50 mm) which passed between the electrodes through the operating gas. The obtained results, presented in the form of images, which illustrated the two-dimensional distributions of NO molecule concentration in the non-thermal reactor, showed that the corona discharge-induced removal of NO molecules occurred not only in the vicinity of the plasma region formed by the corona discharge-induced removal of NO molecules occurred not only in the vicinity of the plasma region formed by the corona streamers and in the downstream region of the reactor but also in the upstream region of the reactor, i.e. before the flue gas simulator has entered the plasma region. This information obtained owing to the LIF technique, is important for the understanding of the plasma-chemistry processes responsible for NOx decomposition in non-thermal plasma reactors and for optimising their performance.

Photochemical modification of polymeric materials and the polarization of light in ionomeric guest/host systems

NASA Astrophysics Data System (ADS)

Pan, Bo

Photochemical methods were introduced to develop important extrusion processes, through which polymers can either be functionalized or modified by altering molecular weight characteristics. Therefore, poly(methyl methacrylate) (PMMA) incorporated with a small amount of light-reactive functional groups was synthesized. These functional groups can be activated by UV irradiation in a post extrusion process to produce high molecular weight polymer and/or crosslinked polymer. Environmental stress cracking resistance of these polymers was examined and correlated to damping using dynamic mechanic analysis. To improve industrial reactive extrusion process of preparing maleic anhydride grafted polypropylene (MAR-g-PP), photografting was proposed and studied. Using benzophenone (BP) as the initiator, grafting efficiency was significantly improved compared to peroxide initiated grafting. Moreover, nearly constant conversion of maleic anhydride was observed in photografting. The high efficiency of benzophenone initiated photografting was attributed to the formation of the excited triplet state maleic anhydride. A rate constant of 6.0*109 M-1*sec-1 for the quenching of triplet state BP with MAH was obtained using laser photolysis spectroscopy. In a comparison, the hydrogen abstraction process from polypropylene by the triplet state BP molecules has a rate constant of 4.1*105 M-1*sec-1. In solution grafting with the use of benzene as the solvent, a facile triplet state energy transfer process may also occur leading to the formation of the excited triplet state MAH. Spectroscopic methods involving light were also used for the study of the guest-host interactions in polymer systems. The use of ionomers as the matrix for the oriented guest/host systems, cationic dye systems in particular, was shown to enhance polarization efficiency as well as dye uptake as comparing to conventional polymers, such as poly(vinyl alcohol). It was found that the dye molecules in carboxylated EVOH (EVOH-COONa) have higher degree of orientation than in EVOH, while polymer chain orientation is quite similar in these two polymers. The difference in the dye orientation was attributed to the ion-ion interactions between dye molecules and carboxylate groups of the modified polymer.

Paintable band-edge liquid crystal lasers.

PubMed

Gardiner, Damian J; Morris, Stephen M; Hands, Philip J W; Mowatt, Carrie; Rutledge, Rupert; Wilkinson, Timothy D; Coles, Harry J

2011-01-31

In this paper we demonstrate photonic band-edge laser emission from emulsion-based polymer dispersed liquid crystals. The lasing medium consists of dye-doped chiral nematic droplets dispersed within a polymer matrix that spontaneously align as the film dries. Such lasers can be easily formed on single substrates with no alignment layers. The system combines the self-organizing periodic structure of chiral nematic liquid crystals with the simplicity of the emulsion procedure so as to produce a material that retains the emission characteristics of band-edge lasers yet can be readily coated. Sequential and stacked layers demonstrate the possibility of achieving simultaneous multi-wavelength laser output from glass, metallic, and flexible substrates.

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.

Thermoelectricity in fullerene-metal heterojunctions.

PubMed

Yee, Shannon K; Malen, Jonathan A; Majumdar, Arun; Segalman, Rachel A

2011-10-12

Thermoelectricty in heterojunctions, where a single-molecule is trapped between metal electrodes, has been used to understand transport properties at organic-inorganic interfaces. (1) The transport in these systems is highly dependent on the energy level alignment between the molecular orbitals and the Fermi level (or work function) of the metal contacts. To date, the majority of single-molecule measurements have focused on simple small molecules where transport is dominated through the highest occupied molecular orbital. (2, 3) In these systems, energy level alignment is limited by the absence of electrode materials with low Fermi levels (i.e., large work functions). Alternatively, more controllable alignment between molecular orbitals and the Fermi level can be achieved with molecules whose transport is dominated by the lowest unoccupied molecular orbital (LUMO) because of readily available metals with lower work functions. Herein, we report molecular junction thermoelectric measurements of fullerene molecules (i.e., C(60), PCBM, and C(70)) trapped between metallic electrodes (i.e., Pt, Au, Ag). Fullerene junctions demonstrate the first strongly n-type molecular thermopower corresponding to transport through the LUMO, and the highest measured magnitude of molecular thermopower to date. While the electronic conductance of fullerenes is highly variable, due to fullerene's variable bonding geometries with the electrodes, the thermopower shows predictable trends based on the alignment of the LUMO with the work function of the electrodes. Both the magnitude and trend of the thermopower suggest that heterostructuring organic and inorganic materials at the nanoscale can further enhance thermoelectric performance, therein providing a new pathway for designing thermoelectric materials.

Tryptophan and ATTO 590: mutual fluorescence quenching and exciplex formation.

PubMed

Bhattacharjee, Ujjal; Beck, Christie; Winter, Arthur; Wells, Carson; Petrich, Jacob W

2014-07-24

Investigation of fluorescence quenching of probes, such as ATTO dyes, is becoming an increasingly important topic owing to the use of these dyes in super-resolution microscopies and in single-molecule studies. Photoinduced electron transfer is their most important nonradiative pathway. Because of the increasing frequency of the use of ATTO and related dyes to investigate biological systems, studies are presented for inter- and intramolecular quenching of ATTO 590 with tryptophan. In order to examine intramolecular quenching, an ATTO 590-tryptophan conjugate was synthesized. It was determined that tryptophan is efficiently quenching ATTO 590 fluorescence by excited-state charge transfer and two charge transfer complexes are forming. In addition, it was discovered that an exciplex (whose lifetime is 5.6 ns) can be formed between tryptophan and ATTO 590, and it is suggested that the possibility of such exciplex formation should be taken into account when protein fluorescence is monitored in a system tagged with ATTO dyes.

Dyes as bifunctional markers of DNA hybridization on surfaces and mutation detection.

PubMed

García-Mendiola, Tania; Cerro, María Ramos; López-Moreno, José María; Pariente, Félix; Lorenzo, Encarnación

2016-10-01

The interaction of small molecules with DNA has found diagnostic and therapeutic applications. In this work, we propose the use of two different dyes, in particular Azure A and Safranine, as bifunctional markers of on-surface DNA hybridization and potent tools for screening of specific gene mutations directly in real DNA PCR amplicons extracted from blood cells. By combining spectroscopic and electrochemical methods we demonstrate that both dyes can interact with single and double stranded DNA to a different extent, allowing reliable hybridization detection. From these data, we have also elucidated the nature of the interaction. We conclude that the binding mode is fundamentally intercalative with an electrostatic component. The dye fluorescence allows their use as nucleic acid stains for the detection of on-surfaces DNA hybridization. Its redox activity is exploited in the development of selective electrochemical DNA biosensors. Copyright © 2016 Elsevier B.V. All rights reserved.

Facile synthesis of fluorescent polymer nanoparticles by covalent modification-nanoprecipitation of amine-reactive ester polymers.

PubMed

Lee, Yeonju; Hanif, Sadaf; Theato, Patrick; Zentel, Rudolf; Lim, Jeewoo; Char, Kookheon

2015-06-01

Emission wavelength control in fluorescent nanoparticles (NPs) is crucial for their applications. In the case of inorganic quantum dots or dye-impregnated silica NPs, such a control is readily achieved by changing the size of the particles or choosing appropriate fluorescent dyes, respectively. A similar modular approach for controlling the emission wavelength of fluo-rescent polymer NPs, however, is difficult. This article reports on fluorescent polymer NPs, the synthesis of which provides a platform for a modular approach towards the preparation of fluorescent NPs of desired emission wavelength. Atom-transfer radical polymerization (ATRP) is employed to synthesize reactive ester polymers, which are then easily modified with a commercially available dye and subsequently subjected to nanoprecipitation. The resulting NPs, with low size polydispersity, show an enhanced emission quantum yield when compared with the same dye molecules in solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organo/Zn-Al LDH Nanocomposites for Cationic Dye Removal from Aqueous Media

NASA Astrophysics Data System (ADS)

Starukh, G.; Rozovik, O.; Oranska, O.

2016-04-01

Cationic dye sorption by Zn-Al-layered double hydroxides (LDHs) modified with anionic surfactants was examined using methylene blue (MB) dye as a compound model in aqueous solutions. The modification of Zn-Al LDHs was performed by reconstruction method using dodecyl sulfate anion (DS) solutions. DS contained Zn-Al LDHs were characterized by XRD, FTIR, thermogravimetric, and SEM analysis. The reconstructed organo/Zn-Al LDHs comprise the crystalline phases (DS-intercalated LDHs, hydrotalcite), and the amorphous phase. The intercalation of DS ions into the interlayer galleries and DS adsorption on the surface of the LDHs occurred causing the MB adsorption on the external and its sorption in the internal surfaces of modified LDHs. The presence of DS greatly increased the affinity of organo/Zn-Al LDHs for MB due to hydrophobic interactions between the surfactants and the dye molecules. The optical properties of sorbed MB were studied.

Quantitative super-resolution localization microscopy of DNA in situ using Vybrant® DyeCycle™ Violet fluorescent probe.

PubMed

Żurek-Biesiada, Dominika; Szczurek, Aleksander T; Prakash, Kirti; Best, Gerrit; Mohana, Giriram K; Lee, Hyun-Keun; Roignant, Jean-Yves; Dobrucki, Jurek W; Cremer, Christoph; Birk, Udo

2016-06-01

Single Molecule Localization Microscopy (SMLM) is a recently emerged optical imaging method that was shown to achieve a resolution in the order of tens of nanometers in intact cells. Novel high resolution imaging methods might be crucial for understanding of how the chromatin, a complex of DNA and proteins, is arranged in the eukaryotic cell nucleus. Such an approach utilizing switching of a fluorescent, DNA-binding dye Vybrant® DyeCycle™ Violet has been previously demonstrated by us (Żurek-Biesiada et al., 2015) [1]. Here we provide quantitative information on the influence of the chemical environment on the behavior of the dye, discuss the variability in the DNA-associated signal density, and demonstrate direct proof of enhanced structural resolution. Furthermore, we compare different visualization approaches. Finally, we describe various opportunities of multicolor DNA/SMLM imaging in eukaryotic cell nuclei.

Quantitative super-resolution localization microscopy of DNA in situ using Vybrant® DyeCycle™ Violet fluorescent probe

PubMed Central

Żurek-Biesiada, Dominika; Szczurek, Aleksander T.; Prakash, Kirti; Best, Gerrit; Mohana, Giriram K.; Lee, Hyun-Keun; Roignant, Jean-Yves; Dobrucki, Jurek W.; Cremer, Christoph; Birk, Udo

2016-01-01

Single Molecule Localization Microscopy (SMLM) is a recently emerged optical imaging method that was shown to achieve a resolution in the order of tens of nanometers in intact cells. Novel high resolution imaging methods might be crucial for understanding of how the chromatin, a complex of DNA and proteins, is arranged in the eukaryotic cell nucleus. Such an approach utilizing switching of a fluorescent, DNA-binding dye Vybrant® DyeCycle™ Violet has been previously demonstrated by us (Żurek-Biesiada et al., 2015) [1]. Here we provide quantitative information on the influence of the chemical environment on the behavior of the dye, discuss the variability in the DNA-associated signal density, and demonstrate direct proof of enhanced structural resolution. Furthermore, we compare different visualization approaches. Finally, we describe various opportunities of multicolor DNA/SMLM imaging in eukaryotic cell nuclei. PMID:27054149

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.

Calcium Sensitive Fluorescent Dyes Fluo-4 and Fura Red under Pressure: Behaviour of Fluorescence and Buffer Properties under Hydrostatic Pressures up to 200 MPa.

PubMed

Schneidereit, D; Vass, H; Reischl, B; Allen, R J; Friedrich, O

2016-01-01

The fluorescent Ca2+ sensitive dyes Fura Red (ratiometric) and Fluo-4 (non-ratiometric) are widely utilized for the optical assessment of Ca2+ fluctuations in vitro as well as in situ. The fluorescent behavior of these dyes is strongly depends on temperature, pH, ionic strength and pressure. It is crucial to understand the response of these dyes to pressure when applying calcium imaging technologies in the field of high pressure bioscience. Therefore, we use an optically accessible pressure vessel to pressurize physiological Ca2+-buffered solutions at different fixed concentrations of free Ca2+ (1 nM to 25.6 μM) and a specified dye concentration (12 μM) to pressures of 200 MPa, and record dye fluorescence intensity. Our results show that Fluo-4 fluorescence intensity is reduced by 31% per 100 MPa, the intensity of Fura Red is reduced by 10% per 100 MPa. The mean reaction volume for the dissociation of calcium from the dye molecules [Formula: see text] is determined to -17.8 ml mol-1 for Fluo-4 and -21.3 ml mol-1 for Fura Red. Additionally, a model is presented that is used to correct for pressure-dependent changes in pH and binding affinity of Ca2+ to EGTA, as well as to determine the influence of these changes on dye fluorescence.

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.

Near-infrared fluorescence imaging using organic dye nanoparticles.

PubMed

Yu, Jia; Zhang, Xiujuan; Hao, Xiaojun; Zhang, Xiaohong; Zhou, Mengjiao; Lee, Chun-Sing; Chen, Xianfeng

2014-03-01

Near-infrared (NIR) fluorescence imaging in the 700-1000 nm wavelength range has been very attractive for early detection of cancers. Conventional NIR dyes often suffer from limitation of low brightness due to self-quenching, insufficient photo- and bioenvironmental stability, and small Stokes shift. Herein, we present a strategy of using small-molecule organic dye nanoparticles (ONPs) to encapsulate NIR dyes to enable efficient fluorescence resonance energy transfer to obtain NIR probes with remarkably enhanced performance for in vitro and in vivo imaging. In our design, host ONPs are used as not only carriers to trap and stabilize NIR dyes, but also light-harvesting agent to transfer energy to NIR dyes to enhance their brightness. In comparison with pure NIR dyes, our organic dye nanoparticles possess almost 50-fold increased brightness, large Stokes shifts (∼250 nm) and dramatically enhanced photostability. With surface modification, these NIR-emissive organic nanoparticles have water-dispersity and size- and fluorescence- stability over pH values from 2 to 10 for almost 60 days. With these superior advantages, these NIR-emissive organic nanoparticles can be used for highly efficient folic-acid aided specific targeting in vivo and ex vivo cellular imaging. Finally, during in vivo imaging, the nanoparticles show negligible toxicity. Overall, the results clearly display a potential application of using the NIR-emissive organic nanoparticles for in vitro and in vivo imaging. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

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.

Time-resolved fluorescence polarization spectroscopy of visible and near infrared dyes in picosecond dynamics

NASA Astrophysics Data System (ADS)

Pu, Yang; Alfano, Robert R.

2015-03-01

Near-infrared (NIR) dyes absorb and emit light within the range from 700 to 900 nm have several benefits in biological studies for one- and/or two-photon excitation for deeper penetration of tissues. These molecules undergo vibrational and rotational motion in the relaxation of the excited electronic states, Due to the less than ideal anisotropy behavior of NIR dyes stemming from the fluorophores elongated structures and short fluorescence lifetime in picosecond range, no significant efforts have been made to recognize the theory of these dyes in time-resolved polarization dynamics. In this study, the depolarization of the fluorescence due to emission from rotational deactivation in solution will be measured with the excitation of a linearly polarized femtosecond laser pulse and a streak camera. The theory, experiment and application of the ultrafast fluorescence polarization dynamics and anisotropy are illustrated with examples of two of the most important medical based dyes. One is NIR dye, namely Indocyanine Green (ICG) and is compared with Fluorescein which is in visible range with much longer lifetime. A set of first-order linear differential equations was developed to model fluorescence polarization dynamics of NIR dye in picosecond range. Using this model, the important parameters of ultrafast polarization spectroscopy were identified: risetime, initial time, fluorescence lifetime, and rotation times.

Does the position of the electron-donating nitrogen atom in the ring system influence the efficiency of a dye-sensitized solar cell? A computational study.

PubMed

Biswas, Abul Kalam; Barik, Sunirmal; Das, Amitava; Ganguly, Bishwajit

2016-06-01

We have reported a number of new metal-free organic dyes (2-6) that have cyclic asymmetric benzotripyrrole derivatives as donor groups with peripheral nitrogen atoms in the ring, fluorine and thiophene groups as π-spacers, and a cyanoacrylic acid acceptor group. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were employed to examine the influence of the position of the donor nitrogen atom and π-conjugation on solar cell performance. The calculated electron-injection driving force (ΔG inject), electron-regeneration driving force (ΔG regen), light-harvesting efficiency (LHE), dipole moment (μ normal), and number of electrons transferred (∆q) indicate that dyes 3, 4, and 6 have significantly higher efficiencies than reference dye 1, which exhibits high efficiency. We also extended our comparison to some other reported dyes, 7-9, which have a donor nitrogen atom in the middle of the ring system. The computed results suggest that dye 6 possesses a higher incident photon to current conversion efficiency (IPCE) than reported dyes 7-9. Thus, the use of donor groups with peripheral nitrogen atoms appears to lead to more efficient dyes than those in which the nitrogen atom is present in the middle of the donor ring system. Graphical Abstract The locations of the nitrogen atoms in the donor groups in the designed dye molecules have an important influence on DSSC efficiency.

Photostability effect of silica nanoparticles encapsulated fluorescence dye

NASA Astrophysics Data System (ADS)

Ahmad, Atiqah; Zakaria, Nor Dyana; Razak, Khairunisak Abdul

2017-12-01

Fluorescence dyes are based on small organic molecules have become of interest in chemical biology and widely used for cell and intracellular imaging. However, fluorescence dyes have limitations such as photo bleaching, poor photochemical stability and has a short Stokes shift. It is less valuable for long-term cell tracking strategies and has very short lifetime. In order to overcome the problems, dye-incorporated nanomaterials become of interest. Nanomaterials encapsulation provides a protection layer around the fluorescence dye which improves the stability of fluorescence dye. In this study, silica nanoparticles encapsulated with 1,1%-dioctadecyl-3,3,3%,3%-tetramethylindocarbocyanine perchlorate (Dil) was successfully synthesised by using micelle entrapment method to investigate the effect of encapsulation of nanoparticles towards the properties of fluorescent dye. The synthesised nanoparticles (SiDil) was characterised by particle size analyser, Transmission Electron Microscopy (TEM), UV-Vis spectrometer and Fluorescent spectrometer. Observation using TEM showed spherical shape of nanoparticles with 53 nm diameter. Monodispersed and well nanoparticles distribution was confirmed by low polydispersity index of 0.063 obtained by particle size analyser. Furthermore, the photoluminescence properties of the SiDil were evaluated and compared with bare Dil dye. Both SiDil and bare Dil was radiated under 200 W of Halogen lamp for 60 minutes and the absorbance intensity was measured using UV-Vis spectrometer. The result showed more stable absorbance intensity for SiDil compared to bare Dil dye, which indicated that Si nanoparticles encapsulation improved the photostability property.

Rapid and efficient detection of single chromophore molecules in aqueous solution

NASA Astrophysics Data System (ADS)

Li, Li-Qiang; Davis, Lloyd M.

1995-06-01

The first experiments on the detection of single fluorescent molecules in a flowing stream of an aqueous solution with high total efficiency are reported. A capillary injection system for sample delivery causes all the dye molecules to pass in a diffusion-broadened stream within a fast-moving sheath flow, through the center of the tightly focused laser excitation beam. Single-molecule detection with a transit time of approximately 1 ms is accomplished with a high-quantum-efficiency single-photon avalanche diode and a low dead-time time-gating circuit for discrimination of Raman-scattered light from the solvent.

Solvatochromic and Fluorogenic Dyes as Environment-Sensitive Probes: Design and Biological Applications.

PubMed

Klymchenko, Andrey S

2017-02-21

Fluorescent environment-sensitive probes are specially designed dyes that change their fluorescence intensity (fluorogenic dyes) or color (e.g., solvatochromic dyes) in response to change in their microenvironment polarity, viscosity, and molecular order. The studies of the past decade, including those of our group, have shown that these molecules become universal tools in fluorescence sensing and imaging. In fact, any biomolecular interaction or change in biomolecular organization results in modification of the local microenvironment, which can be directly monitored by these types of probes. In this Account, the main examples of environment-sensitive probes are summarized according to their design concepts. Solvatochromic dyes constitute a large class of environment-sensitive probes which change their color in response to polarity. Generally, they are push-pull dyes undergoing intramolecular charge transfer. Emission of their highly polarized excited state shifts to the red in more polar solvents. Excited-state intramolecular proton transfer is the second key concept to design efficient solvatochromic dyes, which respond to the microenvironment by changing relative intensity of the two emissive tautomeric forms. Due to their sensitivity to polarity and hydration, solvatochromic dyes have been successfully applied to biological membranes for studying lipid domains (rafts), apoptosis and endocytosis. As fluorescent labels, solvatochromic dyes can detect practically any type of biomolecular interactions, involving proteins, nucleic acids and biomembranes, because the binding event excludes local water molecules from the interaction site. On the other hand, fluorogenic probes usually exploit intramolecular rotation (conformation change) as a design concept, with molecular rotors being main representatives. These probes were particularly efficient for imaging viscosity and lipid order in biomembranes as well as to light up biomolecular targets, such as antibodies, aptamers and receptors. The emerging concepts to achieve fluorogenic response to the microenvironment include ground-state isomerization, aggregation-caused quenching, and aggregation-induced emission. The ground-state isomerization exploits, for instance, polarity-dependent spiro-lactone formation in silica-rhodamines. The aggregation-caused quenching uses disruption of the self-quenched dimers and nanoassemblies of dyes in less polar environments of lipid membranes and biomolecules. The aggregation-induced emission couples target recognition with formation of highly fluorescent dye aggregates. Overall, solvatochromic and fluorogenic probes enable background-free bioimaging in wash-free conditions as well as quantitative analysis when combined with advanced microscopy, such as fluorescence lifetime (FLIM) and ratiometric imaging. Further development of fluorescent environment-sensitive probes should address some remaining problems: (i) improving their optical properties, especially brightness, photostability, and far-red to near-infrared operating range; (ii) minimizing nonspecific interactions of the probes in biological systems; (iii) their adaptation for advanced microscopies, notably for superresolution and in vivo imaging.

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.

High-repetition-rate, narrow-band dye lasers with water as a solvent for dyes

NASA Astrophysics Data System (ADS)

Ray, Alok K.; Sinha, Sucharita; Kundu, Soumitra; Kumar, Sasi; Nair, Sivagiriyal Karunakaran Sreenivasan; Pal, Tamal; Dasgupta, Kamalesh

2002-03-01

The performance of a copper vapor laser-pumped narrow-band dye laser in oscillator-amplifier configuration with water-based binary mixture solvents is described. Although oscillator efficiency in water-surfactant (sodium lauryl sulfate) solvent was comparable with that that employed pure ethanolic solvent, amplifier efficiency was found to be lower. Experiments that were carried out with vertically polarized pump beams and either horizontally or vertically polarized signal beams show that, in case of both the pump and signal having orthogonal polarization (horizontal) and same polarization (vertical), the extraction efficiency for both ethanolic and water-micelle media increased substantially from 15.7% to 18.5% and from 10% to 12.5%, respectively. However, the relative difference remained nearly the same, indicating that a slower orientational diffusion of excited dye molecules in a micellar medium is not responsible for a decrease in amplifier efficiency. Amplifier efficiency comparable with that containing ethanolic dye solutions could be obtained with a binary solvent that comprises a mixture of water and about 30% n-propanol. The performances of two efficient dyes, Rhodamine-6G and Kiton Red S, using water-based solvents were studied.