Quartz crystal microbalance monitoring of density changes in mesoporous TiO2 phytate films during redox and ion exchange processes

Nanofilm deposits of TiO2 nanoparticle phytates are formed on gold electrode surfaces by 'directed assembly' methods. Alternate exposure of a 3-mercapto-propionic acid modified gold surface to (i) a TiO2 sol and (ii) an aqueous phytic acid solution (pH 3) results in layer-by-layer formation of a mesoporous film. Ru(NH3)(6)(3+) is shown to strongly adsorb/accumulate into the mesoporous structure whilst remaining electrochemically active. Scanning the electrode potential into a sufficiently negative potential range allows the Ru(NH3)(6)(3+) complex to be reduced to Ru(NH3)(6)(2+) which undergoes immediate desorption. When applied to a gold coated quartz crystal microbalance (QCM) sensor, electrochemically driven adsorption and desorption processes in the mesoporous structure become directly detectable as a frequency response, which corresponds directly to a mass or density change in the membrane. The frequency response (at least for thin films) is proportional to the thickness of the mass-responsive film, which suggests good mechanical coupling between electrode and film. Based on this observation, a method for the amplified QCM detection of small mass/density changes is proposed by conducting measurements in rigid mesoporous structures. (C) 2003 Elsevier Science B.V. All rights reserved.

Redox chemistry and electronic properties of 2,3,5,6-tetrakis(2-pyridyl)pyrazine-bridged diruthenium complexes controlled by N,C,N '-biscyclometalated ligands

To investigate the consequences of cyclometalation for electronic communication in dinuclear ruthenium complexes, a series of 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) bridged diruthenium complexes was prepared and studied. These complexes have a central tppz ligand bridging via nitrogen-to-ruthenium coordination bonds, while each ruthenium atom also binds either a monoanionic, N,C,N'-terdentate 2,6-bis(2'-pyridyl)phenyl (R-N boolean AND C boolean AND N) ligand or a 2,2':6',2 ''-terpyridine (tpy) ligand. The N,C,N'-, that is, biscyclometalation, instead of the latter N,N', N ''-bonding motif significantly changes the electronic properties of the resulting complexes. Starting from well-known [{Ru(tpy)}(2)(mu-tppz)](4+) (tpy = 2,2':2 '',6-terpyridine) ([3](4+)) as a model compound, the complexes [{Ru(R-N boolean AND C boolean AND N)}(mu-tppz){Ru(tpy)}](3+) (R-N boolean AND C(H)boolean AND N = 4-R-1,3-dipyridylbenzene, R = H ([4a](3+)), CO2Me ([4b](3+))), and [{Ru(R-N boolean AND C boolean AND N)}(2)(mu-tppz)](2+), (R = H ([5a](2+)), CO2Me ([5b](2+))) were prepared with one or two N,C,N'-cyclometalated terminal ligands. The oxidation and reduction potentials of cyclometalated [4](3+) and [5](2+) are shifted negatively compared to non-cyclometalated [3](4+), the oxidation processes being affected more significantly. Compared to [3](4+), the electronic spectra of [5](2+) display large bathochromic shifts of the main MLCT transitions in the visible spectral region with low-energy absorptions tailing down to the NIR region. One-electron oxidation of [3](4+) and [5](2+) gives rise to low-energy absorption bands. The comproportionation constants and NIR band shape correspond to delocalized Robin-Day class III compounds. Complexes [4a](3+) (R = H) and [4b](3+) (R = CO2Me) also exhibit strong electronic communication, and notwithstanding the large redox-asymmetry the visible metal-to-ligand charge-transfer absorption is assigned to originate from both metal centers. The potential of the first, ruthenium-based, reversible oxidation process is strongly negatively shifted. On the contrary, the second oxidation is irreversible and cyclometalated ligand-based. Upon one-electron oxidation, a weak and low-energy absorption arises.

Chemical modification of a nanocrystalline TiO(2) film for efficient electric connection of glucose oxidase

A novel biosensor for glucose was prepared by adsorption of 1,1`-bis(4-carboxybenzyl)-4,4`-bipyridinium di-bromide compound (H(2)BpybcBr(2)) onto the surface of a nanocrystalline TiO(2) film deposited onto FTO glasses, which was used as a platform to assemble the enzyme glucose oxidase to the electrode surface. The H(2)BpybcBr(2)/TiO(2)/FTO modified electrode was characterized by scanning electron microscopy, X-ray fluorescence image, cyclic voltammograms and spectroelectrochemical measurements. The immobilization of GOD on functionalized TiO(2) film led to stable amperometric biosensing for glucose with a linear range from 153 mu mol L(-1) to 1.30 mmol L(-1) and a detection limit of 51 mu mol L(-1). The apparent Michaelis-Menten constant (K(m)) was estimated to be 3.76 mmol L(-1), which suggested a high enzyme-substrate affinity. The maximum electrode sensitivity was 1.25 mu A mmol L(-1). The study proved that the combination of viologen mediators with TiO(2) film retains the electrocatalytic activity of the enzyme, and also enhances the electron transfer process, and hence regenerating the enzyme in the reaction with glucose. (C) 2010 Elsevier Inc. 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.

The Fabrication and Characterization of a Nickel Nanoparticle Modified Boron Doped Diamond Electrode for Electrocatalysis of Primary Alcohol Oxidation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Regeneration of poly-L-lysine modified carbon electrodes in the accumulation and cathodic stripping voltammetric determination of the cromoglycate anion

Cromoglycate is accumulated on a poly-L-lysine (PLL) modified carbon electrode best from pH 4 solution, where it is anionic and the PLL is cationic, and at which pH the cromoglycate gives a good reduction peak at -0.82 V. The PLL film can be regenerated readily by washing the electrode with 3 M sodium hydroxide solution, in which the PLL is deprotonated. Regeneration of the film is not required as frequently when larger amounts of PLL are incorporated into it. This allows standard addition procedures to be carried out without regenerating the electrode. Linear calibration graphs have been obtained typically in the range 0.1 - 1.5 mug ml(-1). Detection limits have been calculated to be 10 ng ml(-1). The standard addition method has been applied satisfactorily to diluted urine solutions. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Propriedades analíticas e eletroanalíticas de um silsesquioxano nanoestruturado organofuncionalizado

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Desenvolvimento de biossensor baseado em extrato de açaí e sensor biomimético para detecção de hexazinona

Pós-graduação em Química - IQ

Nanostructured screen-printed electrodes modified with self-assembled monolayers for determination of metronidazole in different matrices

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Microelectrode array in mixed alkanethiol self-assembled monolayers: Electrochemical studies

We report an efficient alternative to obtain recessed microelectrodes device on gold electrode surface, in which mixed self-assembled monolayer of long and short carbon alkanethiol chains was used for this purpose. Development of the modified electrodes included the chemical adsorption of 11-mercaptoundecanoic acid and 2-mercaptoethanol solution, as well as their mixtures, on gold surface, resulting in the final mixed self-assembled monolayer configuration. For comparison, the electrochemical performance of self-assembled monolayer of 11-mercaptoundecanoic acid. 3-mercaptopropionic acid, 4-mercapto-1-butanol and 6-mercapto-1-hexanol modified electrodes was also investigated. It was verified that, in the mixed self-assembled monolayer, the 11-mercaptoundecanoic acid acts as a barrier for electron transfer while the short alkanethiol chair is deposited in an island-like shape through which electrons can be freely transferred to ions in solution, allowing electrochemical reactions to occur. The performance of the modified electrodes toward microelectrode behavior was investigated via cyclic voltammetry and electrochemical impedance spectroscopy measurements using [Fe(CN)(6)](3-/4-) redox couple as a probe. In this case, sigmoidal voltammetric responses were obtained, very similar to those observed for microelectrodes. Such behavior reinforces the proposition of electron transfer through the short alkanethiol chain layer and surface blockage by the long chain one. Electrochemical impedance results allowed calculated the mean radius value of each microelectrode disks of 3.8 mu m with about 22 mu m interval between them. The microelectrode environment provided by the mixed self-assembled monolayer can be conveniently used to provide an efficient catalytic conversion in biosensing applications. (C) 2012 Elsevier Ltd. All rights reserved.

Classification of suppressor additives based on synergistic and antagonistic ensemble effects

Three fundamental types of suppressor additives for copper electroplating could be identified by means of potential Transient measurements. These suppressor additives differ in their synergistic and antagonistic interplay with anions that are chemisorbed on the metallic copper surface during electrodeposition. In addition these suppressor chemistries reveal different barrier properties with respect to cupric ions and plating additives (Cl, SPS). While the type-I suppressor selectively forms efficient barriers for copper inter-diffusion on chloride-terminated electrode surfaces we identified a type-II suppressor that interacts non-selectively with any kind of anions chemisorbed on copper (chloride, sulfate, sulfonate). Type-I suppressors are vital for the superconformal copper growth mode in Damascene processing and show an antagonistic interaction with SPS (Bis-Sodium-Sulfopropyl-Disulfide) which involves the deactivation of this suppressor chemistry. This suppressor deactivation is rationalized in terms of compositional changes in the layer of the chemisorbed anions due to the competition of chloride and MPS (Mercaptopropane Sulfonic Acid) for adsorption sites on the metallic copper surface. MPS is the product of the dissociative SPS adsorption within the preexisting chloride matrix on the copper surface. The non-selectivity in the adsorption behavior of the type-II suppressor is rationalized in terms of anion/cation pairing effects of the poly-cationic suppressor and the anion-modified copper substrate. Atomic-scale insights into the competitive Cl/MPS adsorption are gained from in situ STM (Scanning Tunneling Microscopy) using single crystalline copper surfaces as model substrates. Type-III suppressors are a third class of suppressors. In case of type-land type-II suppressor chemistries the resulting steady-state deposition conditions are completely independent on the particular succession of additive adsorption. In contrast to that a strong dependence of the suppressing capabilities on the sequence of additive adsorption ("first comes, first serves" principle) is observed for the type-IIIsuppressor. This behavior:is explained by a suppressor barrier that impedes not only the copper inter-diffusion but also the transport of other additives (e.g. SPS) to the copper surface. (C) 2011 Elsevier Ltd. All rights reserved.

An in-situ surface electrochemistry approach toward whole-cell studies: Charge transfer between Geobacter sulfurreducens and electrified metal/electrolyte interfaces through linker molecules

Electrochemical reactivity and structure properties of electrogenic bacteria, Geobacter sulfurreducens (Gs) were studied to explore the heterogeneous electron transfer at the bacteria/electrode interface using electrochemical and in-situ spectroscopic techniques. The redox behavior of Gs adsorbed on a gold electrode, which is modified with a ω-functionalized self-assembled monolayer (SAM) of alkanethiols, depends strongly on the terminal group. The latter interacts directly with outermost cytochromes embedded into the outer membrane of the Gs cells. The redox potential of bacterial cells bound electrostatically to a carboxyl-terminated SAM is close to that observed for bacteria attached to a bare gold electrode, revealing a high electronic coupling at the cell/SAM interface. The redox potentials of bacterial cells adsorbed on amino- and pyridyl-terminated SAMs are significantly different suggesting that the outermost cytochromes changes their conformation upon adsorption on these SAMs. No redox activity of Gs was found with CH3-, N(CH3)3+- and OH-terminated SAMs. Complementary in-situ spectroscopic studies on bacteria/SAMs/Au electrode assemblies were carried out to monitor structure changes of the bacterial cells upon polarization. Spectro-electrochemical techniques revealed the electrochemical turnover of the oxidized and reduced states of outer membrane cytochromes (OMCs) in Gs, providing evidence that the OMCs are responsible for the direct electron transfer to metal electrodes, such as gold or silver, during the electricity production. Furthermore, we observed spectroscopic signatures of the native structure of the OMCs and no conformational change during the oxidation/reduction process of the microorganisms. These findings indicate that the carboxyl-anchoring group provides biocompatible conditions for the outermost cytochromes of the Gs, which facilitate the heterogeneous electron transfer at the microorganism/electrode interface.

Characterization of the Capacitance of a Rotating Ring–Disk Electrode

The use of rotating ring–disk electrodes as generator-collector systems has so far been limited to the detection of Faradaic currents at the ring. As opposed to other generator-collector configurations, non-Faradaic detection has not yet been carried out with rotating ring–disk electrodes. In this study, a.c. perturbation based detection for measurement of the ring impedance is introduced. By using a conducting polymer-modified disk electrode in combination with a bare gold ring as a model, it is shown that the measured ring capacitance correlates with the polarization of the polymer film, most probably due to counter-ion exchange. A method of calculating the ring capacitance based on a small-signal sinusoid perturbation is described and the most important instrumental limitations are identified.

Proton-transfer compounds of isnipecotamide with the aromatic dicarboxylic acids 4-nitrophthalic, 4,5-dichlorophthalic, 5-nitroisophthalic and terephthalic acid

The structures of the 1:1 proton-transfer compounds of isonipecotamide (4-piperidinecarboxamide) with 4-nitrophthalic acid, 4-carbamoylpiperidinium 2-carboxy-4-nitrobenzoate, C6H13N2O8+ C8H4O6- (I), 4,5-dichlorophthalic acid, 4-carbamoylpiperidinium 2-carboxy-4,5-dichlorobenzoate, C6H13N2O8+ C8H3Cl2O4- (II) and 5-nitroisophthalic acid, 4-carbamoylpiperidinium 3-carboxy-5-nitrobenzoate, C6H13N2O8+ C8H4O6- (III) as well as the 2:1 compound with terephthalic acid, bis(4-carbamoylpiperidinium)benzene-1,2-dicarboxylate dihydrate, 2(C6H13N2O8+) C8H4O42- . 2H2O (IV)have been determined at 200 K. All salts form hydrogen-bonded structures, one-dimensional in (II) and three-dimensional in (I), (III) and (IV). In (I) and (III) the centrosymmetric R2/2(8) cyclic amide-amide association is found while in (IV) several different types of water-bridged cyclic associations are present [graph sets R2/4(8), R3/4(10), R4/4(12), R3/3(18) and R4/6(22)]. The one-dimensional structure of (I), features the common 'planar' hydrogen 4,5-dichlorophthalate anion together with enlarged cyclic R3/3(13) and R3/4(17) associations. With the structures of (I) and (III) the presence of head-to-tail hydrogen phthalate chain substructures is found. In (IV) head-to-tail primary cation-anion associations are extended longitudinally into chains through the water-bridged cation associations and laterally by piperidinium N-H...O(carboxyl) and water O-H...O(carboxyl) hydrogen bonds. The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen-bonded structures. An additional example of cation--anion association with this cation is also shown in the asymmetric three-centre piperidinium N-H...O,O'(carboxyl) interaction in the first-reported structure of a 2:1 isonipecotamide-carboxylate salt.

4-(4-Aminophenylsulfonyl)aniline-1,3-5-trinitrobenzene (1/2)

The asymmetric unit of the title co-crystalline 1:2 adduct C12H12N2O2 . 2(C6H3N3O6) contains two independent molecules of bis(4-aminophenyl)sulfone (the drug Dapsone) and four molecules of 1,3,5-trinitrobenzene and is extended into a two-dimensional hydrogen-bonded network structure through amino N-H...O hydrogen-bonding associations with nitro O- atom acceptors. In the two independent Dapsone molecules the inter-ring dihedral angles are 69.0(2) and 63.59(11)deg. Aromatic pi-pi interactions are also found between one of the Dapsone aromatic rings and a trinitrobenzene ring [minimum ring centroid separation 3.576(5)Ang.]. A 4-aminophenyl ring moiety of one of the Dapsone molecules and two nitro groups of a trinitrobenzene are disordered in a 50:50 ratio.