Phototransients of 2-ethylaminodiphenylborinate generated by direct photolysis and photosensitization

Ground state interactions and excited states and transients formed after photolysis and photosensitization of 2-ethylaminodiphenylborinate (2APB) were studied by various techniques. The UV spectrum shows a large absorption band at 235 nm (epsilon = 14,500 M-1 cm(-1)) with a shoulder at 260 nm. The fluorescence spectra show increasing emission intensity with maximum at 300 nm, which shifts to the red up to 10(-3) M concentrations. At higher concentrations, the emission intensity decreases, probably due to the formation of aggregates. UV excitation in deareated solutions shows the formation of two transients at 300 and 360 nm. The latter has a lifetime of 5.7 mu s in ethanol and is totally quenched in the presence of oxygen and assigned to the triplet state of 2APB. The 300 nm peak is not affected by oxygen, has a lifetime in the order of milliseconds, and corresponds to a boron-centered radical species originated from the singlet state. A boron radical can also be obtained by electron transfer from triplet Safranine to the borinate (k(q) = 9.7 x 10(7) M-1 s(-1)) forming the semioxidized form of the dye. EPR experiments using DMPO show that dye-sensitized and direct UV-photolysis of 2ABP renders initially arylboron-centered radicals. (C) 2012 Elsevier B.V. All rights reserved.

A three-component protocol for the enantiodifferentiation of amines using triphenyl borate and BINOL: is it an ion pair or an amine-coordinated complex?

The structure of the borate complex responsible for the enantiodifferentiation of amines using a previously reported three-component protocol has been established. The choice between an ion pair and an amine-coordinated complex with the N atom of the amine coordinated to the B atom is favored for the former structure based on the DFT-calculated B-11 NMR chemical shifts. In contrast to expectations, the anisotropies of the quadrupolar B-11 nucleus for the two structures were calculated to be indistinguishable with regard to their effect on the linewidth of the NMR signal. (C) 2014 Elsevier Ltd. All rights reserved.

Borax Mediated Layer-by-Layer Self-Assembly of Neutral Poly(vinyl alcohol) and Chitosan

We report a multilayer film of poly(vinyl alcohol) (PVA)-borate complex and chitosan by using a layer-by-layer approach. PVA is an uncharged polymer, but hydroxyl functional groups of PVA can be crosslinked by using borax as a cross-linking agent. As a result electrostatic charges and intra- and interchain cross-links are introduced in the PVA chain and provide physically cross-linked networks. The PVA-borate was then deposited on a flat Substrate as well as on colloidal particles with chitosan as an oppositely charged polyelectrolyte. Quartz crystal microbalance. scanning electron microscopy, and atomic force microscopy were used to follow the growth of thin film oil flat substrate. Analogous experiments were performed on melamine formaldehyde colloidal particles (3-3.5 mu m) to quantify the process for the preparation of hollow rnicrocapsules. Removal of the core in 0.1 N HCI results in hollow microcapsules. Characterization of microcapsules by transmission electron microscopy revealed formation of stable microcapsules. Further, self-assembly of PVA-borate/chitosan was loaded with the anticancer drug doxorubicin, and release rates were determined at different pH Values to highlight the drug delivery potential of this system.

Particle flux studies of sediment traps from the northern and equatorial Indian Ocean

The Asian monsoon system governs seasonality and fundamental environmental characteristics in the study area from which two distinct peculiarities are most notable: upwelling and convective mixing in the Arabian Sea and low surface salinity and stratification in the Bay of Bengal due to high riverine input and monsoonal precipitation. The respective oceanography sets the framework for nutrient availability and productivity. Upwelling ensures high nitrate concentration with temporal/spatial Si limitation; freshwater-induced stratification leads to reduced nitrogen input from the subsurface but Si enrichment in surface waters. Ultimately, both environments support high abundance of diatoms, which play a central role in the export of organic matter. It is speculated that, additional to eddy pumping, nitrogen fixation is a source of N in stratified waters and contributes to the low-d15N signal in sinking particles formed under riverine impact. Organic carbon fluxes are best correlated to opal but not to carbonate, which is explained by low foraminiferal carbonate fluxes within the river-impacted systems. This observation points to the necessity of differentiating between carbonate sources for carbon flux modeling. As evident from a compilation of previously published and new data on labile organic matter composition (amino acids and carbohydrates), organic matter fluxes are mainly driven by direct input from marine production, except the site off Pakistan where sedimentary input of (marine) organic matter is dominant during the NE monsoon. The explanation of apparently different organic carbon export efficiency calls for further investigations of, for example, food web structure and water column processes.

Improved efficiency of organic light-emitting diodes based on a europium complex by fluorescent dye

Improved efficiency of organic light-emitting diodes (OLEDs) based on europium complexes have been realized by using a fluorescent dye 4-(dicyanomethylene)-2-t-butyl-6 (1,1,7,7-tetramethyljulolidyl-9-enyl))-4H-pyran (DCJTB) doping. The luminous efficiency of the devices with a fluorescent dye in the emissive layer was found to improve two times of that in devices without fluorescent dye. The devices showed pure red light, which is the characteristic emission of trivalent europium ion with a full-width at half-maximum of 3 nm. The maximum brightness and luminous efficiency reached 1200 cd/m(2) at 23 V and 7.3 cd/A (2.0 Im/w), respectively, at a current density of 0.35 mA/cm(2).

Improved efficiency by a fluorescent dye in red organic light-emitting devices based on a europium complex

By doping a fluorescent dye in the emissive layer, we realized high efficient red organic light-emitting diodes (OLEDs) based on a europium complex. The OLEDs realized by this method showed pure red emission at 612 nm with a full width at half maximum Of 3 nm. The Commission International de L'Eclairage Coordination keeps approximately the same as the emission of pure Eu3+. The maximum brightness and EL efficiency reached 2450 cd/m(2) at 20 V and 9.0 cd/A (6.0 lm/w) at a current density of 0.012 mA/cm(2), respectively. At the brightness of 100 cd/m(2), the current efficiency reached 4.4 cd/A.

Synchronous fluorescence and UV–vis spectroscopic studies of interactions between the tetracycline antibiotic, aluminium ions and DNA with the aid of the Methylene Blue dye probe

Synchronous fluorescence spectroscopy (SFS) was applied for the investigation of interactions of the antibiotic, tetracycline (TC), with DNA in the presence of aluminium ions (Al3+). The study was facilitated by the use of the Methylene Blue (MB) dye probe, and the interpretation of the spectral data with the aid of the chemometrics method, parallel factor analysis (PARAFAC). Three-way synchronous fluorescence analysis extracted the important optimum constant wavelength differences, Δλ, and showed that for the TC–Al3+–DNA, TC–Al3+ and MB dye systems, the associated Δλ values were different (Δλ = 80, 75 and 30 nm, respectively). Subsequent PARAFAC analysis demonstrated the extraction of the equilibrium concentration profiles for the TC–Al3+, TC–Al3+–DNA and MB probe systems. This information is unobtainable by conventional means of data interpretation. The results indicated that the MB dye interacted with the TC–Al3+–DNA surface complex, presumably via a reaction intermediate, TC–Al3+–DNA–MB, leading to the displacement of the TC–Al3+ by the incoming MB dye probe.

Study of the interaction between 10-hydroxycamptothecine and DNA with the use of ethidium bromide dye as a fluorescence probe

The interaction of 10-hydroxycamptothecine (HCPT) with DNA under pseudo-physiological conditions (Tris-HCl buffer of pH 7.4), using ethidium bromide (EB) dye as a probe, was investigated with the use of spectrofluorimetry, UV-vis spectrometry and viscosity measurement. The binding constant and binding number for HCPT with DNA were evaluated as (7.1 ± 0.5) × 104 M-1 and 1.1, respectively, by multivariate curve resolution-alternating least squares (MCR-ALS). Moreover, parallel factor analysis (PARAFAC) was applied to resolve the three-way fluorescence data obtained from the interaction system, and the concentration information for the three components of the system at equilibrium was simultaneously obtained. It was found that there was a cooperative interaction between the HCPT-DNA complex and EB, which produced a ternary complex of HCPT-DNA-EB. © 2011 Elsevier B.V.

Dinuclear Ru-Cu complexes : electronic characterisation and application to dye-sensitised solar cells

Dye-sensitised solar cells have emerged as an important developing technology for low-cost solar energy conversion and a crucial element of these is the dye, responsible for light harvesting and control of interfacial electron-transfer processes.[1] A number of examples of dye exist in the literature which link a ruthenium polypyridyl complex to another platinum group metal complex such as Ru (II), Os (II), Re (I) or Rh (III) via a bridging ligand.[2-6] These systems are often referred to as heterosupramolecular triads when adsorbed on the surface of TiO2 as the semiconductor becomes an active component in the system. A number of problems can arise with these types of sensitisers, for example if a flexible linker, e.g. bis-pyridylethane, is used to couple the two complexes it can be hard to control the orientation of the whole dye. This may lead to the resultant dye cation hole being closer to the surface than desired, and hence the long-lived charge-separated state is not achieved. In addition the size of these dyes may be much larger than that of a mononuclear complex and can lead to poor pore filling on the TiO2 and lower dye coverage, leading to a lower efficiency cell.[7] Despite these issues, efficient charge-separation has been achieved with polynuclear complexes and a long-lived state on the millisecond timescale has been observed for a trinuclear ruthenium complex.[8]

Increased charge transfer of Poly (ethylene oxide) based electrolyte by addition of small molecule and its application in dye-sensitized solar cells

A Poly (ethylene oxide) based polymer electrolyte impregnated with 2-Mercapto benzimidazole was comprehensively characterized by XRD, UV–visible spectroscopy, FTIR as well as electrochemical impedance spectroscopy. It was found that the crystallization of PEO was dramatically reduced and the ionic conductivity of the electrolyte was increased 4.5 fold by addition of 2-Mercapto benzimidazole. UV–visible and FTIR spectroscopes indicated the formation of charge transfer complex between 2-Mercapto benzimidazole and iodine of the electrolyte. Dye-sensitized solar cells with the polymer electrolytes were assembled. It was found that both the photocurrent density and photovoltage were enhanced with respect to the DSC without 2-Mercapto benzimidazole, leading to a 60% increase of the performance of the cell.

Mössbauer effect and electron paramagnetic resonance studies on zinc borate glasses containing transition metal oxides

Studies have been carried out in glasses containing Fe2O3, V2O5, and Fe2O3 + V2O5. Mossbauer studies in the ZnO-B2O3-Fe2O3 system show that iron is present as Fe3+ with tetrahedral coordination and that the isomer shift and the quadrupole splitting decrease with increase of Fe2O3 Content; similarly, the isomer shift and quadrupole splitting are also found to decrease with increasing ZnO. On the other hand, in the Na2O-ZnO-B2O3-Fe2O3 system, the isomer shift increases with Na2O or ZnO while the quadrupole splitting is fairly insensitive. Electron paramagnetic resonance in the ZnO-B2O3-Fe2O3 system shows signals at g = 4.20 and 2.0, whose intensity and linewidth show strong dependence on Fe2O3 content. In the ZnO-B2O3-V2O5 system, electron paramagnetic resonance shows that vanadium is present as the vanadyl complex, and the hyperfine coupling constants, A(parallel-to) and A(perpendicular-to) decrease with increasing V2O5 content; on the other hand, g(parallel-to) decreases and g(perpendicular-to) increases slightly, indicating an increase in tetragonal distortion. Zinc borate glasses containing Fe2O3 + V2O5 do not show the hyperfine structure of V4+ due to the interaction between Fe3+ and V4+

Heterogeneity in Dye-TiO2 Interactions Dictate Charge Transfer Efficiencies for Diketopyrrolopyrrole-Based Polymer Sensitized Solar Cells

Power conversion efficiency of a solar cell is a complex parameter which usually hides the molecular details of the charge generation process. For rationally tailoring the overall device efficiency of the dye-sensitized solar cell, detailed molecular understanding of photoinduced reactions at the dye-TiO2 interface has to be achieved. Recently, near-IR absorbing diketopyrrolopyrrole-based (DPP) low bandgap polymeric dyes with enhanced photostabilities have been used for TiO2 sensitization with moderate efficiencies. To improve the reported device performances, a critical analysis of the polymerTiO(2) interaction and electron transfer dynamics is imperative. Employing a combination of time-resolved optical measurements complemented by low temperature EPR and steady-state Raman spectroscopy on polymerTiO(2) conjugates, we provide direct evidence for photoinduced electron injection from the TDPP-BBT polymer singlet state into TiO2 through the C-O group of the DPP-core. A detailed excited state description of the electron transfer process in films reveals instrument response function (IRF) limited (<110 fs) charge injection from a minor polymer fraction followed by a picosecond recombination. The major fraction of photoexcited polymers, however, does not show injection indicating pronounced ground state heterogeneity induced due to nonspecific polymerTiO(2) interactions. Our work therefore underscores the importance of gathering molecular-level insight into the competitive pathways of ultrafast charge generation along with probing the chemical heterogeneity at the nanoscale within the polymerTiO2 films for optimizing photovoltaic device efficiencies.

Optical recording properties of metal-azo dye as recording medium with super-resolution near-field structure

A novel metallized azo dye has been synthesized. The absorption spectra of the thin film and thermal characteristic are measured. Static optical recording properties with and without the Bi mask layer super-resolution near-field structure (Super-RENS) of the metal-azo dye are investigated. The results show that the metal-azo dye film has a broad absorbance band in the region of 450-650 nm and the maximum absorbance wavelength is located at 603 nm. It is also found that the new metallized azo dye occupies excellent thermal stability, initiatory decomposition temperature is at 270 degrees C and the mass loss is about 48% in a narrow temperature region (15 degrees C). The complex refractive index N (N = n + ik) is measured. High refractive index (n = 2.45) and low extinction coefficient (k = 0.2) at the recording wavelength 650nm are attained. Static optical recording tests with and without Super-RENS are carried out using a 650nm semiconductor diode laser with recording power of 7mW and laser pulse duration of 200ns. The AFM images show that the diameter of recording mark on the dye film with the Bi mask layer is reduced about 42%, compared to that of recorded mark on the dye film without Super-RENS. It is indicated that Bi can well performed as a mask layer of the dye recording layer and the metallized azo dye can be a promising candidate for recording media with the super-resolution near-field structure.