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At least 127 records · Page 7

Preferential Direction of Electron Transfers at a Dye–Metal Oxide Interface with an Insulating Fluorinated Self-Assembled Monolayer and MgO

Slowing non-desirable electron transfer reactions at metal oxide-dye interfaces is important for many technologies. Specifically, after an interfacial photoinduced charge separation event at a metal oxide-dye interface, it is critically important to limit the rate of electron transfer reactions back to sensitizers and to limit electron transfer reactions between the electrolyte and the metal oxide. Ruthenium-based dyes at metal oxide interfaces are widely used in many fields; however, these dyes often have poor surface insulation resulting in fast recombination kinetics with transition metal-based redox shuttles in an electrolyte. This work explores two semiconductor surface modification strategies designed to minimize recombination events of electrons in TiO 2 with oxidized redox shuttles using a fluorinated siloxane insulator (PFTS) and a metal oxide insulator (MgO) with a well-known Ru dye, B11. Additionally, the influence of these treatments on the rate and duration of photoinduced interfacial charge separation at the TiO 2 -dye interface was examined. The TiO 2 -dye-redox shuttle systems were studied via dye-sensitized solar cell current-voltage curve, incident photon-to-current conversion efficiency, small-modulated photovoltage transient, time-correlated single photon counting, and transient absorption spectroscopy measurements. MgO was found to decrease the rate of the electron transfer reaction from the metal oxide to the electrolyte, decrease the rate of the electron transfer reaction to the oxidized dye from TiO 2 , increase the electron transfer reaction rate from a reduced redox shuttle to an oxidized dye, and decrease the electron injection rate from the photoexcited dye to TiO2. Interestingly, PFTS was found to desirably improve on these rates relative to MgO or untreated TiO 2 . Here, a model based on electrostatic interactions is presented to explain the exceptional behavior of PFTS with DFT computational analysis of PFTS supporting this model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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

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

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A novel porous anionic metal–organic framework with pillared double-layer structure for selective adsorption of dyes

A novel porous anionic metal–organic framework, (Me{sub 2}NH{sub 2}){sub 2}[Zn{sub 2}L{sub 1.5}bpy]·2DMF (BUT-201; H{sub 4}L=4,8-disulfonaphthalene-2,6-dicarboxylic acid; bpy=4,4-bipyridine; DMF=N,N-dimethylformamide), with pillared double-layer structure has been synthesized through the reaction of a sulfonated carboxylic acid ligand and Zn(NO{sub 3}){sub 2}·6H{sub 2}O with 4,4-bipyridine as a co-ligand. It is found that BUT-201 can rapidly adsorb cationic dyes with a smaller size such as Methylene Blue (MB) and Acriflavine Hydrochloride (AH) by substitution of guest (CH{sub 3}){sub 2}NH{sub 2}{sup +}, but has no adsorption towards the cationic dyes with a lager size such as Methylene Violet (MV), the anionic dyes like C. I. Acid Yellow 1 (AY1) and neutral dyes like C. I. Solvent Yellow 7 (SY7), respectively. The results show that the adsorption behavior of BUT-201 relates not only to the charge but also to the size/shape of dyes. Furthermore, the adsorbed dyes can be gradually released in the methanol solution of LiNO{sub 3}. - Graphical abstract: A porous anionic metal–organic framework (BUT-201) can selectively adsorb the cationic dyes by cationic guest molecule substitution, and the adsorbed dyes can be gradually released in the methanol solution of LiNO{sub 3}. - Highlights: • An anionic metal-organic framework (BUT-201) has been synthesized and characterized. • BUT-201 has a three-dimensional (3D) pillared double-layer structure. • BUT-201 can selectively and rapidly adsorb cationic dyes. • The adsorbed dyes can be gradually released in the methanol solution of LiNO{sub 3}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of nickel–zinc ferrite magnetic nanoparticle and dye degradation using photocatalytic ozonation

Graphical abstract: Display Omitted Highlights: ► Nickel–zinc ferrite magnetic nanoparticle (NZFMN) was synthesized and characterized. ► Dye degradation by photocatalytic ozonation using NZFMN was studied. ► Formate, acetate and oxalate were detected as dominant dye degradation aliphatic intermediates. ► Nitrate, sulfate and chloride ions were detected as mineralization products of dyes. ► NZFMN was an effective magnetic nanocatalyst to degrade dyes. -- Abstract: In this paper, nickel–zinc ferrite magnetic nanoparticle (NZFMN) was synthesized and its dye degradation ability using photocatalytic ozonation was investigated. The NZFMN was characterized by X-ray diffraction (XRD), scanning electron microscopic (SEM), Fourier transforms infrared (FTIR) and alternative gradient force magnetometer (AGFM). Reactive Red 198 (RR198) and Direct Green 6 (DG6) were used as dye models. UV–vis and ion chromatography (IC) analyses were employed to study dye degradation. The effects of operational parameters on decolorization such as NZFMN dosage, dye concentration, salt and pH were studied. RR198 and DG6 were completely decolorized (100%) by photocatalytic ozonation using NZFMN. Formate, acetate and oxalate anions were detected as dominant aliphatic intermediates. Nitrate, sulfate and chloride ions were detected as mineralization products of dyes. Results showed that the photocatalytic ozonation using NZFMN was a very effective method for dye degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Substituent Location on the Relationship between the Transition Dipole Moments, Difference Static Dipole, and Hydrophobicity in Squaraine Dyes for Quantum Information Devices

Aggregates of organic dyes that exhibit excitonic coupling have a wide array of applications, including medical imaging, organic photovoltaics, and quantum information devices. The optical properties of a dye monomer, as a basis of dye aggregate, can be modified to strengthen excitonic coupling. Squaraine (SQ) dyes are attractive for those applications due to their strong absorbance peak in the visible range. While the effects of substituent types on the optical properties of SQ dyes have been previously examined, the effects of various substituent locations have not yet been investigated. In this study, density functional theory (DFT) and time-dependent density functional theory (TD-DFT) were used to investigate the relationships between SQ substituent location and several key properties of the performance of dye aggregate systems, namely, difference static dipole (Δd), transition dipole moment (μ), hydrophobicity, and the angle (θ) between Δd and μ. We found that attaching substituents along the long axis of the dye could increase μ while placement off the long axis was shown to increase Δd and reduce θ. The reduction in θ is largely due to a change in the direction of Δd as the direction of μ is not significantly affected by substituent position. Hydrophobicity decreases when electron-donating substituents are located close to the nitrogen of the indolenine ring. These results provide insight into the structure–property relationships of SQ dyes and guide the design of dye monomers for aggregate systems with desired properties and performance.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Degradation characteristic of monoazo, diazo and anthraquinone dye by UV/H{sub 2}O{sub 2} process

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 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 H{sub 2}O{sub 2} photolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication and characterization of ZnO:In thin film as photoanode for DSSC using natural fruit dyes

Dye synthesized solar cell (DSSC) is the third generation solar cell and is considered as low cost solar cell as it does not involved neither complicated fabrication process nor expensive materials. DSSC is made of two conductive glasses, photoanode, counter electrode, electrolyte and dye. Previously, majority of the researchers have been using titanium dioxide and ruthenium as the photoanode and dye respectively. This project is carried out to produce a lower cost DSSC by using natural fruit as the dye and exploring the potential of zinc oxide (ZnO) and indium (In) as the photoanode. The morphology of the thin film surfaces were analyzed using scanning electron microscopy which shows that the increment of indium dopant changes the rough surface texture of the thin film and directly reduces the empty spaces between the particles. Theoretically, this structure can help to reduce the light reflection on the solar cell surface. The thin ZnO:In films are immersed in 3 different fruit dyes (plum, apple and orange). The electrical properties of the DSSCs are displayed in the I-V curves and from this research, it shows that the highest efficiency of DSSC is gained from the dopant combination of ZnO{sub 0.8}In{sub 0.2} for all the dyes. The best efficiency of this research is the DSSC using plum dye with 0.34% compared to apple dye and orange dye which give 0.23% and 0.19% respectively.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Ground and excited state properties of high performance anthocyanidin dyes-sensitized solar cells in the basic solutions

The aglycones of anthocyanidin dyes were previously reported to form carbinol pseudobase, cis-chalcone, and trans-chalcone due to the basic levels. The further investigations of ground and excited state properties of the dyes were characterized using density functional theory with PCM(UFF)/B3LYP/6-31+G(d,p) level in the basic solutions. However, to the best of our knowledge, the theoretical investigation of their potential photosensitizers has never been reported before. In this paper, the theoretical photovoltaic properties sensitized by dyes have been successfully investigated including the electron injections, the ground and excited state oxidation potentials, the estimated open circuit voltages, and the light harvesting efficiencies. The results prove that the electronic properties represented by dyes’ LUMO-HOMO levels will affect to the photovoltaic performances. Cis-chalcone dye is the best anthocyanidin aglycone dye with the electron injection spontaneity of −1.208 eV, the theoretical open circuit voltage of 1.781 V, and light harvesting efficiency of 56.55% due to the best HOMO-LUMO levels. Moreover, the ethanol solvent slightly contributes to the better cell performance than the water solvent dye because of the better oxidation potential stabilization in the ground state as well as in the excited state. These results are in good agreement with the known experimental report that the aglycones of anthocyanidin dyes in basic solvent are the high potential photosensitizers for dye-sensitized solar cell.

74 ATOMIC AND MOLECULAR PHYSICS↗

Insight into the optoelectronic properties of designed solar cells efficient tetrahydroquinoline dye-sensitizers on TiO 2 (101) surface: first principles approach

Seven ‘lead’ dye-sensitizers from Tetrahydroquinoline (THQ) family were proposed and designed based on the structural attributes via quantitative-structure property relationship (QSPR) modeling. They were screened rationally through different computational approaches to explore their potential applications as photosensitizers for dye-sensitized solar cells (DSSCs). Compelling photophysical properties such as electron injection driving force, electron injection time, and dye regeneration were studied for the isolated dyes under the DFT and TD-DFT frameworks. Index of spatial extent (S, D, and Δq), the strength of charge transfer and separation along with the charge transfer process is explored. First principle approach including van der Waals density functional calculation of dye@TiO 2 interface indicates that all of the designed dyes have optimal interfacial behavior. Bader charge analysis, partial density of state (PDOS), charge density and electrostatic potential difference calculation confirms that THQ7 and THQ9 are the most efficient dye-sensitizers. The other five designed dyes also possess the required properties to emerge as effective dye-sensitizers potentially better than those already utilized.

14 SOLAR ENERGY↗

Effect of acidity on the energy level of curcumin dye extracted from Curcuma longa L

The purpose of this research is to investigate the effect of acidity on the energy level of curcumin dye. The natural dye, curcumin, was synthesized from Curcuma longa L. using a simple extraction technique. The purification of curcumin dye was conducted in a column of chromatography and its characteristics were studied. Next, the purified curcumin dye was added by benzoic acids until various acidities of 3.0, 3.5, 4.0, 4.5, and 5.0. The absorbance spectra and the functionality groups found in the dyes were detected by ultraviolet-visible spectroscopy and Fourier-transform infrared spectroscopy, respectively. Meanwhile, the energy level of the dyes, E{sub HOMO} and E{sub LUMO} was measured by cyclic voltammetry. The best energy level of curcumin dye was achieved at pH 3.5 where E{sub red} = −0.37V, E{sub LUMO} = −4.28 eV, E{sub ox} = 1.15V, E{sub HOMO} = −5.83 eV, and E{sub band} {sub gap} = 1.55 eV. Therefore, the purified curcumin dye added by benzoic acid was promising for sensitizing the dye-sensitized solar cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Method of Making Dye-Doped Polystyre Microparticles

Various embodiments provide dye-doped polystyrene microspheres generated using dispersion polymerization. Polystyrene microspheres may be doped with fluorescent dyes, such as xanthene derivatives including kiton red 620 (KR620), using dispersion polymerization. Certain functionalities, such as sodium styrene sulfonate, may be used to shift the equilibrium distribution of dye molecules to favor incorporation of the dye into the particles. Polyelectrolyte materials, such as poly(diallyldimethyl ammonium chloride), PolyDADMAC, may be used to electrostatically trap and bind dye molecules within the particles. A buffer may be used to stabilize the pH change of the solution during dye-doped polystyrene microsphere generation and the buffer may be selected depending on the pKa of the dye being incorporated. The various embodiments may provide dye-doped polystyrene microspheres, such as KR620-doped polystyrene microspheres that are non-toxic and non-carcinogenic. These non-toxic and non-carcinogenic dye-doped polystyrene microspheres may be suitable for use in wind tunnel testing.

Wohl, Jr., Christopher J.↗

Reactive Dye Adsorption from Aqueous Solution on HPEI-Modified Fe{sub 3}O{sub 4} Nanoparticle as a Superadsorbent: Characterization, Modeling, and Optimization

In this work, the optimum condition for the adsorption of Reactive Blue 19 dye onto Fe{sub 3}O{sub 4} functionalized with hyperbranched polyethylenimine (Fe@HPEI) was determined using response surface methodology. The properties of synthesized magnetic Fe@HPEI nanoparticles were ascertained using FTIR, SEM, TEM, VSM and zeta potential measurement. The experimental adsorption data indicating the positive effect of adsorbent dose and contact time, and the negative effect of pH, initial dye concentration and ionic strength on dye adsorption. At optimal condition; pH 3.4, contact time 25 min, adsorbent dose 0.4 g/L and initial dye concentration 113 mg/L, Fe@HPEI nanoparticles removed dye up to 99.27%. The maximum experimental dye adsorption was near to the predicted value of 100%, which confirmed the reliability of the selected statistical model. The dye adsorption data were fitted well to Langmuir isotherm and pseudo-second-order kinetic, and the maximum adsorption capacity was 500 mg/g. Totally, Fe@HPEI as an effective superadsorbent can be repeatedly utilized for the adsorption of dye from the aqueous environment.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Variation in Optoelectronic Properties of Azo Dye-Sensitized TiO 2 Semiconductor Interfaces with Different Adsorption Anchors: Carboxylate, Sulfonate, Hydroxyl and Pyridyl Groups

The optoelectronic properties of four azo dye-sensitized TiO2 interfaces are systematically studied as a function of a changing dye anchoring group: carboxylate, sulfonate, hydroxyl, and pyridyl. The variation in optoelectronic properties of the free dyes and those in dye/TiO 2 nanocomposites are studied both experimentally and computationally, in the context of prospective dye-sensitized solar cell (DSSC) applications. Experimental UV/vis absorption spectroscopy, cyclic voltammetry, and DSSC device performance testing reveal a strong dependence on the nature of the anchor of the optoelectronic properties of these dyes, both in solution and as dye/TiO2 nanocomposites. First-principles calculations on both an isolated dye/TiO2 cluster model (using localized basis sets) and each dye modeled onto the surface of a 2D periodic TiO2 nanostructure (using plane wave basis sets) are presented. Detailed examination of these experimental and computational results, in terms of light harvesting, electron conversion and photovoltaic device performance characteristics, indicates that carboxylate is the best anchoring group, and hydroxyl is the worst, whereas sulfonate and pyridyl groups exhibit competing potential. Different sensitization solvents are found to affect critically the extent of dye adsorption achieved in the dye-sensitization of the TiO2 semiconductor, especially where the anchor is a pyridyl group.

anchor↗

Identification Of Natural Dyes On Archaeological Textile Objects Using Laser Induced Fluorescent Technique

This study aims to evaluate the use of Laser Fluorescent as a non-destructive technique for identification of natural dyes on archaeological textile objects. In this study wool textile samples were dyed with 10 natural dyes such as cochineal, cutch, henna, indigo, Lac, madder, safflower, saffron, sumac and turmeric. These dyes common present on archaeological textile objects to be used as standard dyed textile samples. These selected natural dyes will be used as known references that can be used a guide to identify unknown archaeological dyes. The dyed textile samples were investigated with laser radiation in different wavelengths to detect the best wavelengths for identification each dye. This study confirms that Laser Florescent is very useful and a rapid technique can be used as a non-destructive technique for identification of natural dyes on archaeological textile objects. The results obtained with this study can be a guide for all conservators in identification of natural organic dyes on archaeological textile objects.

36 MATERIALS SCIENCE↗

First principles DFT study of dye-sensitized CdS quantum dots

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 positions 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.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synthesis and characterization of natural red dye from Caesalpinia sappan linn

The study reports the synthesis and characterization of natural red dye. The dyes were extracted from woods of Caesalpiniasappanlinn at varied temperatures of 70, 80, 90, and 100°C for three hours. The dry wood chips and water at a ratio of 6:1 were immersed in the reactor of 150 liters. The absorbance spectra of the natural red dyes were measured by ultra-violet-visible spectroscopy. Meanwhile, Fourier transform infrared spectroscopy was used to investigate the functional groups of the natural red dyes. In addition, the basic production cost was calculated and the fastness property towards cotton fabrics was investigated according to the Indonesia national standard of 105-C06:2010, 105-B01:2010, and 0288-2008. The results showed that the functional groups found the extracted red dyes indicated the complex bond of brazilein with peak absorbance at a wavelength of 538-540 nm. The extraction temperature also changed the functional group of brazilein. From the color, the absorbance peak, the functional groups, and the main production cost, the best parameter to synthesize the natural red dyes from Caesalpiniasappanlinn was at a temperature of 80°C for two hours. Moreover, the natural red dyes has the fastness to wash resistance, light resistance, and scrub resistance by 4-5, 4, and 3-4, respectively. However, further studies for synthesis the natural red dyes by using a continuous reactor are required to identify the naturally complex compounds in brazilein for improving the fastness properties and for reducing the cost.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stimulated Raman scattering of laser dye mixtures dissolved in multiple scattering media

Stimulated Raman scattering (SRS) of a mixture of rhodamine 6G and pyrromethene 605 laser dyes in vesicular films is studied. It is shown that a peculiar interaction of dyes occurs under conditions of multiple scattering of light from vesicles. This interaction manifests itself as SRS excitation of one of the dyes by random lasing of the other dye, provided that the random lasing spectrum overlaps the Stokes lines of the first dye. In addition, there is energy transfer between molecules of these dyes if their luminescence and absorption spectra overlap. The results obtained confirm that the mechanism of SRS from laser dyes in multiple scattering media is similar to that in coherent-active Raman spectroscopy. These results extend the possibility of determining the vibrational spectrum of dye molecules from their secondary radiation in these media. (nonlinear optical phenomena)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterizing the marker-dye correction for Gafchromic EBT2 film: A comparison of three analysis methods

Purpose: Gafchromic EBT2 film has a yellow marker dye incorporated into the active layer of the film that can be used to correct the film response for small variations in thickness. This work characterizes the effect of the marker-dye correction on the uniformity and uncertainty of dose measurements with EBT2 film. The effect of variations in time postexposure on the uniformity of EBT2 is also investigated. Methods: EBT2 films were used to measure the flatness of a {sup 60}Co field to provide a high-spatial resolution evaluation of the film uniformity. As a reference, the flatness of the {sup 60}Co field was also measured with Kodak EDR2 films. The EBT2 films were digitized with a flatbed document scanner 24, 48, and 72 h postexposure, and the images were analyzed using three methods: (1) the manufacturer-recommended marker-dye correction, (2) an in-house marker-dye correction, and (3) a net optical density (OD) measurement in the red color channel. The field flatness was calculated from orthogonal profiles through the center of the field using each analysis method, and the results were compared with the EDR2 measurements. Uncertainty was propagated through a dose calculation for each analysis method. The change in the measured field flatness for increasing times postexposure was also determined. Results: Both marker-dye correction methods improved the field flatness measured with EBT2 film relative to the net OD method, with a maximum improvement of 1% using the manufacturer-recommended correction. However, the manufacturer-recommended correction also resulted in a dose uncertainty an order of magnitude greater than the other two methods. The in-house marker-dye correction lowered the dose uncertainty relative to the net OD method. The measured field flatness did not exhibit any unidirectional change with increasing time postexposure and showed a maximum change of 0.3%. Conclusions: The marker dye in EBT2 can be used to improve the response uniformity of the film. Depending on the film analysis method used, however, application of a marker-dye correction can improve or degrade the dose uncertainty relative to the net OD method. The uniformity of EBT2 was found to be independent of the time postexposure.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗