Structure effects of self-assembled Prussian blue confined in highly organized mesoporous TiO(2) on the electrocatalytic properties towards H(2)O(2) detection

Here we report the derivatization of mesoporous TiO(2) thin films for the preparation of H(2)O(2) amperometric sensors. The coordination of the bifunctional ligand 1,10 phenantroline, 5,6 dione on the surface Ti(IV) ions provides open coordination sites for Fe(II) cations which are the starting point for the growth of a layer of Prussian blue polymer. The porous structure of the mesoporous TiO(2) allows the growth, ion by ion of the coordination polymer. Up to four layer of Prussian blue can be deposit without losing the porous structure of the film, which results in an enhanced response of these materials as H(2)O(2) sensors. These porous confined PB modified electrodes are robust sensors that exhibit good reproducibility, environmental stability and high sensitivity towards H(2)O(2) detection. (C) 2010 Elsevier B.V. All rights reserved.

On the pH dependence of electroactivity of poly(methylene blue) films

The electrochemical behavior of poly(methylene blue) on different electrodes has been investigated by electrochemical quartz crystal microbalance and in situ spectrophotometric measurements coupled to cyclic voltammetry. Polymeric films were obtained potentiodynamically and the charge transport mechanism was analyzed. The electrochemical results show that polymer electroactivity depends not only on pH but also on the substrate. Charge compensation changes with both pH and the size of the anions showing a transition in the pH range of polymer pKa. It was demonstrated by spectroelectrochemical experiments that the electroactivity of the film depends on the radical/radical cation equilibrium. The potentials where the most electroactive species are formed have been determined. (C) 2009 Elsevier Ltd. All rights reserved.

Optical properties of red, green and blue emitting rare earth benzenetricarboxylate compounds

Red, blue and green emitting rare earth compounds (RE(3+) = Eu(3+), Gd(3+) and Tb(3+)) containing the benzenetricarboxylate ligands (BTC) [hemimellitic (EMA), trimellitic (TLA) and trimesic (TMA)] were synthesized and characterized by elemental analysis, complexometric titration, X-ray diffraction patterns, thermogravimetric analysis and infrared spectroscopy. The complexes presented the following formula: [RE(EMA)(H(2)O)(2)], [RE(TLA)(H(2)O)(4)] and [RE(TMA)(H(2)O)(G)], except for Tb-TMA compound, which was obtained only as anhydrous. Phosphorescence data of Gd(3+)-(BTC) complexes showed that the triplet states (T) of the BTC(3-) anions have energy higher than the main emitting states of the Eu(3+) ((5)D(0)) and Tb(3+) ((5)D(4)), indicating that BTC ligands can act as intramolecular energy donors for these metal ions. The high values of experimental intensity parameters (Omega(2)) of Eu(3+)-(BTC) complexes indicate that the europium ion is in a highly polarizable chemical environment. Based on the luminescence spectra, the energy transfer from the T state of BTC ligands to the excited (5)D(0) and (5)D(4) levels of the Eu(3+) and Tb(3+) ions is discussed. The emission quantum efficiencies (eta) of the (5)D(0) emitting level of the Eu(3+) ion have been also determined. In the case of the Tb(3+) ion, the photoluminescence data show the high emission intensity of the characteristic transitions (5)D(4) -> (7)F(J) (J=0-6), indicating that the BTC ligands are good sensitizers. The RE(3+)-(BTC) complexes act as efficient light conversion molecular devices (LCMDs) and can be used as tricolor luminescent materials. (C) 2009 Elsevier B.V. All rights reserved.

Sequential injection analysis (SIA) and response surface methodology: A versatile small volume approach for optimization of photo-Fenton processes

Optimization of photo-Fenton degradation of copper phthalocyanine blue was achieved by response surface methodology (RSM) constructed with the aid of a sequential injection analysis (SIA) system coupled to a homemade photo-reactor. Highest degradation percentage was obtained at the following conditions [H(2)O(2)]/[phthalocyanine] = 7, [H(2)O(2)]/[FeSO(4)] = 10, pH = 2.5, and stopped flow time in the photo reactor = 30 s. The SIA system was designed to prepare a monosegment containing the reagents and sample, to pump it toward the photo-reactor for the specified time and send the products to a flow-through spectrophotometer for monitoring the color reduction of the dye. Changes in parameters such as reagent molar ratios. residence time and pH were made by modifications in the software commanding the SI system, without the need for physical reconfiguration of reagents around the selection valve. The proposed procedure and system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 97% of the dye was degraded. (C) 2009 Elsevier B.V. All rights reserved.

Fabrication of disposable voltammetric electronic tongues by using Prussian Blue films electrodeposited onto CD-R gold surfaces and recognition of milk adulteration

A new approach to fabricate a disposable electronic tongue is reported. The fabrication of the disposable sensor aimed the integration of all electrodes necessary for measurement in the same device. The disposable device was constructed with gold CD-R and copper sheets substrates and the sensing elements were gold, copper and a gold surface modified with a layer of Prussian Blue. The relative standard deviation for signals obtained from 20 different disposable gold and 10 different disposable copper electrodes was below 3.5%. The performance, electrode materials and the capability of the device to differentiate samples were evaluated for taste substances model, milk with different pasteurization processes (homogenized/pasteurized, ultra high temperature (UHT) pasteurized and UHT pasteurized with low fat content) and adulterated with hydrogen peroxide. In all analysed cases, a good separation between different samples was noticed in the score plots obtained from the principal component analysis (PCA). Crown Copyright (C) 2008 Published by Elsevier B.V. All rights reserved.

Synthesis, characterization and spectroscopic investigation of new tetrakis(acetylacetonato)thulate(III) complexes containing alkaline metals as countercations

In this work a series of tetrakis complexes C[Tm(acac)(4)] where C(+) = Li(+) Na(+) and K(+) countercations and acac = acetylacetonate ligand were synthesized and characterized for photoluminescence investigation The relevant aspect is that these complexes are water-free in the first coordination sphere The emission spectra of the tetrakis Tm(3+)-complexes present narrow bands characteristic of the (1)G(4)->(3)H(6) (479 nm) (1)G(4)->(3)F(4) (650 nm) and (1)G(4) ->(3)H(5) (779 nm) transitions of the Tm(3+) ion with the blue emission color at 479 nm as the most prominent one The lifetime values (tau) of the emitting (1)G(4) level of the C[Tm(acac)(4)] complexes were 344 360 and 400 ns for the Li(+) Na(+) and K(+) countercations respectively showing an increasing linear behavior versus the ionic radius of the alkaline ion An efficient intramolecular energy transfer process from the triplet state (T) of the ligands to the emitting (1)G(4) state of the Tm(3+) ion is observed This fact together with the absence of water molecules in first coordination sphere allows these tetrakis Tm(3+)-complexes to act as efficient blue light conversion molecular devices (c) 2010 Elsevier B V All rights reserved

Photocatalytic degradation of methylene blue by TiO(2)-Cu thin films: Theoretical and experimental study

In this work the effect of doping concentration and depth profile of Cu atoms on the photocatalytic and surface properties of TiO(2) films were studied. TiO(2) films of about 200 nn thickness were deposited on glass substrates on which a thin Cu layer (5 nm) was deposited. The films were annealed during 1 s to 100 degrees C and 400 degrees C, followed by chemical etching of the Cu film. The grazing incidence X-ray fluorescence measurements showed a thermal induced migration of Cu atoms to depths between 7 and 31 nm. The X-ray photoelectron spectroscopy analysis detected the presence of TiO(2), Cu(2)O and Cu(0) phases and an increasing Cu content with the annealing temperature. The change of the surface properties was monitored by the increasing red-shift and absorption of the ultraviolet-visible spectra. Contact angle measurements revealed the formation of a highly hydrophilic surface for the film having a medium Cu concentration. For this sample photocatalytic assays, performed by methylene blue discoloration, show the highest activity. The proposed mechanism of the catalytic effect, taking place on Ti/Cu sites, is supported by results obtained by theoretical calculations. (C) 2010 Elsevier B.V. All rights reserved.

Photocatalyst TiO(2)-Co: the effect of doping depth profile on methylene blue degradation

In this work, we study the effect of doping depth profile on the photocatalytic and surface properties of TiO(2) films. Two thin film layers of TiO(2) (200 nm) and Co (5 nm), respectively, were deposited by physical evaporation on glass substrate. These films were annealed for 1 s at 100 and 400 A degrees C and the Co layer was removed by chemical etching. Atomic force microscopy (AFM) phase images showed changes in the surface in function of thermal treatment. The grazing-incidence X-ray fluorescence (GIXRF) measurements indicated that the thermal treatment caused migration of Co atoms to below the surface, the depths found were between 19 and 29 nm. The contact angle showed distinct values in function of the doped profile or Co surface concentration. The UV-vis spectra presented a red shift with the increasing of thermal treatment. Photocatalytical assays were performed by methylene blue discoloration and the higher activity was found for TiO(2)-Co treated at 400 A degrees C, the ESI-MS showed the fragments formed during the methylene blue decomposition.

Photocatalytic decomposition of methylene blue via Fenton mechanisms by silicon wafer doped with Au and Cu: a theoretical and experimental study

In this work, we studied the photocatalytic and the structural aspects of silicon wafers doped with Au and Cu submitted to thermal treatment. The materials were obtained by deposition of metals on Si using the sputtering method followed by fast heating method. The photocatalyst materials were characterized by synchrotron-grazing incidence X-ray fluorescence, ultraviolet-visible spectroscopy, X-ray diffraction, and assays of H(2)O(2) degradation. The doping process decreases the optical band gap of materials and the doping with Au causes structural changes. The best photocatalytic activity was found for thermally treated material doped with Au. Theoretical calculations at density functional theory level are in agreement with the experimental data.

Heterogeneous photocatalytic degradation of acid dyes in aqueous TiO2 suspensions: Kinetics and toxicity

This work assesses the photocatalytic (TiO2/UV) degradation of a simulated acid dye bath (Yellow 3, Red 51, Blue 74, and auxiliary chemicals). Color and phytotoxicity removal were monitored by spectrophotometry and lettuce (Lactuca sativa) seeds as the test organism, respectively. Mineralization was determined by DOC analyses. Photocatalytic, photolytic, and adsorption experiments were performed, showing that adsorption was negligible. After 240 minutes of irradiation, it was achieved 96% and 78% of color removal with photocatalysis and photolysis, respectively. 37% of mineralization occurred with photocatalysis only. The dye bath was rendered completely non-toxic after 60 minutes of photocatalytic treatment; the same result was only achieved with photolysis after 90 minutes. A kinetic model composed of two first-order in series reactions was used. The first photocatalytic decolorization rate constant was k(1) = 0.062 min(-1) and the second k(2) = 0.0043 min(-1), approximately two times greater than the photolytic ones.

Photocatalytic Decolorization of Commercial Acid Dyes using Solar Irradiation

This work investigates the solar heterogeneous photocatalytic degradation of three commercial acid dyes: Blue 9 (C.I. 42090), Red 51 (C.I. 45430), and Yellow 23 (C.I. 19140). TiO(2) P25 from Degussa was used as the photocatalyst. The dyes were completely degraded within 120 min of treatment in the following increasing order of removal rate: Blue 9 < Yellow 23 < Red 51. The photocatalytic color removal process was well described by a two-first-order in-series reaction, followed by another first-order reaction. Photolytic experiments showed that this process is quite inefficient and highly selective towards Red 51 only. The dyes` solution was completely decolorized and organic matter removals up to 99% were achieved with photocatalysis. The lack of selectivity and the possibility of using solar light to excite the photocatalyst are promising results regarding the feasibility of this technology.

Paper Microzone Plates

This paper describes 96- and 384-microzone plates fabricated in paper as alternatives to conventional multi-well plates fabricated in molded polymers. Paper-based plates are functionally related to plastic well plates, but they offer new capabilities. For example, paper-microzone plates are thin (similar to 180 mu m), require small volumes of sample (5 mu L per zone), and can be manufactured from inexpensive materials ($0.05 per plate). The paper-based plates are fabricated by patterning sheets of paper, using photolithography, into hydrophilic zones surrounded by hydrophobic polymeric barriers. This photolithography used an inexpensive formulation photoresist that allows rapid (similar to 15 min) prototyping of paper-based plates. These plates are compatible with conventional microplate readers for quantitative absorbance and fluorescence measurements. The limit of detection per zone loaded for fluorescence was 125 fmol for fluorescein isothiocyanate-labeled bovine serum albumin, and this level corresponds to 0.02 the quantity of analyte per well used to achieve comparable signal-to-noise in a 96-well plastic plate (using a solution of 25 nM labeled protein). The limits of detection for absorbance on paper was aproximately 50 pmol per zone for both Coomassie Brilliant Blue and Amaranth dyes; these values were 0.4 that required for the plastic plate. Demonstration of quantitative colorimetric correlations using a scanner or camera to image the zones and to measure the intensity of color, makes it possible to conduct assays without a microplate reader.

Ink-Jet Printing of Color Optical Filters for LCD Applications

At the age of multi-media, portable electronic devices such as mobile phones, personal digital assistant and handheld gaming systems have increased the demand for high performance displays with low cost production. Inkjet printing color optical filters (COF) for LCD applications seem to be an interesting alternative to decrease the production costs. The advantage of inkjet printing technology is to be fast, accurate, easy to run and cheaper than other technologies. In this master thesis work, we used various disciplines such as optical microscopy, rheology, inkjet printing, profilometering and colorimetry. The specific aim of the thesis was to investigate the feasibility of using company-A pigment formulation in inkjet production of COF for active matrix LCD applications. Ideal viscosity parameters were determined from 10 to 20mPa·s for easy inkjet printing at room temperature. The red pigments used are fully dispersed into the solvent and present an excellent homogenous repartition after printing. Thickness investigations revealed that the printed COF were equal or slightly thicker than typically manufactured ones. The colorimetry investigations demonstrated color coordinates very close to the NTSC red standard. LED backlighting seems to be a valuable solution to combine with the printed COF regarding to the spectrum and color analysis. The results on this thesis will increase the understanding of inkjet printing company-A pigments to produce COF for LCD applications.

ICC-profilers funktionalitet vid byte av tryckfärgskvalitet

This degree theme work aims to evaluate the present ICC-profile and printing ink of Dalarnas Tidningar AB. The companyhas changed printing ink quality and wants to evaluate how the present ICC-profile work with the new printingink. Four different ICC-profiles were included in the comparison.One test printing was accomplished with two different separations. Two new ICC-profile was created, as a comparingmaterial. An densitometer was used to measure the technical parameters of the printing. IT8-charts and RGB-chartswas measured with spectrophotometer. La*b*-values, CMYK-values, graybalance curves, color deflections and colorgamuts was compared on screen and on the printed material.Materials from an earlier testprinting and evalution, made by Stora Enso Kvarnsveden AB 2003, was used to evaluatethe function of Dalarnas Tidningar AB´s ICC-profile with the present printing ink quality. The IT8-chart from todaystestprinting was oppened in a program for textediting to have access to La*b*- and CMYK values. The values from theearlier testprinting was supplied from Stora Enso Kvarnsveden AB.The result of this work shows that the ICC-profile from the company, compared with de other profiles, reproduce darkershadow regions which can make loss of details. An higher saturation is recieved in the red and yellow area while thegreen and blue area lose its intensity. The profile gave images which are some contrastless and with a flat reproduction.Today printing ink quality gives more saturation and intensity in the yellow and blue area compared with former printingink. The dark tone reproduces with decreased luminance, however.

Vitpunktsförskjutningens påverkan på ICC-profiler vid användande av optiska vitmedel

The connection between fluorescence and color management still is a relatively unexplored area. Thefollowing composition analyses the theory that when printing on fluorescent ink jet paper using ICCprofilesa more yellow print will appear. In theory the ICC-profile compensate for blue light that fluorescefrom the paper with the complementary color, yellow. The human eye apprehands this fluorescentlight as white.When categorizing a number of ink jet qualities some tests to indicate change of color in the final printwere made. Five qualities were chosen for further analyses, each with different white point. TheTC3.5CMYK target was prined on an ink jet printer and measured with different filters for the measurementequipment, GretagMacbeth Spectrolino. U- and UV-filters were used during the testings.From the measurement data ICC-profiles were made to make it possible to watch how the profiles compensatefor the blue change of color that appeared in the data. Although a distinct change of color intoblue were discernible in the measured data there is no evident proof that this cause a final print thatis more yellow. Other conclusions and results are to be read at the end of this composition.