EQCM characterization of self-assembled kinetics of 4-pyridyl hydroquinone at Pt surface and its ion transfer in electrochemical redox

The adsorbed kinetics, proton transportation in electrochemical redox process of 4-pyridyl hydroquinone (4PHQ) self-assembled monolayer (SAM) modified Pt electrode were studied by electrochemical quartz crystal microbalance (EQCM) in situ. It proved that the electrode was modified by a monolayer and underwent a rapid electron transfer. It was a slow adsorbed kinetic process. The ion transfer in the electrochemical redox at the SAM-modified electrode surface mainly involved into the hydrate hydrogen ion.

Electrochemical growth and characterization of polyoxometalate-containing monolayers and multilayers on alkanethiol monolayers self-assembled on gold electrodes

A general strategy has been developed for fabrication of ultrathin monolayer and multilayer composite films composed of nearly all kinds of polyoxometalates (POMs), including isopolyanions (IPAs), and heteropolyanions (HPAs). It involves stepwise adsorption between the anionic POMs and a cationic polymer on alkanethiol (cysteamine and 3-mercaptopropionic acid) self-assembled monolayers (SAMs) based on electrostatic interaction. Here a Keggin-type HPA SiMo11VO405- was chosen as a main representative to elucidate, in detail, the fabrication and characterization of the as-prepared composite films. A novel electrochemical growth method we developed for film formation involves cyclic potential sweeps over a suitable potential range in modifier solutions. It was comparatively studied with a commonly used method of immersion growth, i.e., alternately dipping a substrate into modifier solutions. Growth processes and structural characteristics of the composite films are characterized in detail by cyclic voltammetry, UV-vis spectroscopy (UV-vis), X-ray photoelectron spectroscopy (XPS), micro-Fourier transform infrared reflection-absorption spectroscopy (FTIR-RA), and electrochemical quartz crystal microbalance (EQCM). The electrochemical growth is proven to be more advantageous than the immersion growth. The composite films exhibit well-defined surface waves characteristic of the HPAs' redox reactions. In addition, the composite films by the electrochemical growth show a uniform structure and an excellent stability. Ion motions accompanying the redox processes of SiMo11VO405- in multilayer films are examined by in situ time-resolved EQCM and some results are first reported. The strategy used here has been successfully popularized to IPAs as well as other HPAs no matter what structure and composition they have.

The progress in the method of immobilizing biomolecules for piezoelectric immunosensors

The working principle of piezoelectric mass sensor is generally introduced. Tbe recent progress about the method of immobilizing biomolecule, such as antigen, antibody etc. onto piezoelectric crystal surfaces has been reported, including the way of directly immobilizing biomolecules, and immobilizing them using protein A(or protein G), polymer, silianizition agent, SAM technique, LB monolayer technique etc.. At last, some recent trends of the field has been outlined.

Potential-dependent adsorption/desorption of organic adsorbate at HOPG electrode and accompanying delamination of graphite surface

In situ electrochemical scanning tunneling microscopy, alternating current voltammetry, and electrochemical quartz crystal microbalance have been employed to follow the potential-dependent adsorption/desorption processes of nucleic acid bases on highly oriented pyrolytic graphite (HOPG) electrode. The results show that (i) potential-dependent adsorption/desorption of nucleic acid bases on HOPG electrode was accompanied by delamination of the HOPG surface, and the delamination initiates from steps or kinks on the electrode surface, which provide highly active sites for adsorption; (ii) the delamination usually occurred when the electrode potential was changed or when the electrode was at potentials where the phase transition of adsorbate occurred. These results suggest that the surface stress resulting from the interaction between the substrate and adsorbate, as well as the interaction due to potential-induced surface charge distribution and the hysteresis of charge equilibrium are the main factors resulting in HOPG delamination. (C) 1999 The Electrochemical Society. S0013-4651(97)12-013-4. All rights reserved.

Probe beam deflection study on electrochemically controlled release of 5-fluorouracil

In this paper, the polypyrrole (PPy) film modified electrodes are used as an electroreleasing reservoir. The electrochemically controlled release of 5-fluorouracil (5-FU) from a PPy film modified electrode to aqueous electrolytes is studied by the in situ probe beam deflection (PBD) method combined with cyclic voltammetry (CV) and chronoamperometry (CA). The PBD results reveal that the release of 5-FU from PPy film depends on the electrochemical redox process of the PPy film electrode. The released amount is controlled by the reduction potential and is proportional to the thickness of the film. The exchange of 5-FU anions with Cl- on an open circuit is slow on the time scale of minutes, but the release of 5-FU anions can proceed quickly at -0.6 V (vs Ag/AgCl). The amount of released 5-FU decreases with the time that the PPy film is soaked in aqueous solution. (C) 1998 Elsevier Science Ltd. All rights reserved.

Probe beam deflection combined with cyclic voltammetry studies of C-60-modified electrode film

C-60 films, prepared by solution casting, were studied by means of in situ probe beam deflection (PBD) combined with cyclic voltammetry (CV). PBD is a powerful technique for investigation of phenomena at the electrode/electrolyte interface in acetonitrile with quaternary ammonium and alkali metal salts as supporting electrolytes. In tetra-n-butylammonium (TBA(+)) salt solution, a stable CV can be obtained during the first two reduction/reoxidation waves. On reduction, injection of cations to maintain charge balance and dissolution of small amount of C-60(-) (TEA(+)) and/or C-60(2-) (TBA(+))(2) are detected. During the reoxidation process ejection of cations and injection of anions occur simultaneously, especially for the second reoxidation wave. In the case where TBABr is the supporting electrolyte, the accompanied behavior is more complicated than in TBABF(4), TBAClO(4), and TBAPF(6) solutions. A small pair of prewaves in CV are proposed due to oxidation/reduction of C-60 domains but not dissolution/redeposition of C-60 film. Extending the potential scan range to the third reduction wave, no apparent corresponding reoxidation wave is related to the third reduction wave, the electroactivity of the film disappears rapidly and dissolution of C-60 film is observed. In tetraethylammonium (TEA(+)) and NAClO(4) solutions, the electrochemistry of the C-60 films is unstable, and potential scans lead to dissolution of flaking of the film.

Multi-scale modelling of atomic layer deposition

High-permittivity ("high-k") dielectric materials are used in the transistor gate stack in integrated circuits. As the thickness of silicon oxide dielectric reduces below 2 nm with continued downscaling, the leakage current because of tunnelling increases, leading to high power consumption and reduced device reliability. Hence, research concentrates on finding materials with high dielectric constant that can be easily integrated into a manufacturing process and show the desired properties as a thin film. Atomic layer deposition (ALD) is used practically to deposit high-k materials like HfO2, ZrO2, and Al2O3 as gate oxides. ALD is a technique for producing conformal layers of material with nanometer-scale thickness, used commercially in non-planar electronics and increasingly in other areas of science and technology. ALD is a type of chemical vapor deposition that depends on self-limiting surface chemistry. In ALD, gaseous precursors are allowed individually into the reactor chamber in alternating pulses. Between each pulse, inert gas is admitted to prevent gas phase reactions. This thesis provides a profound understanding of the ALD of oxides such as HfO2, showing how the chemistry affects the properties of the deposited film. Using multi-scale modelling of ALD, the kinetics of reactions at the growing surface is connected to experimental data. In this thesis, we use density functional theory (DFT) method to simulate more realistic models for the growth of HfO2 from Hf(N(CH3)2)4/H2O and HfCl4/H2O and for Al2O3 from Al(CH3)3/H2O.Three major breakthroughs are discovered. First, a new reaction pathway, ’multiple proton diffusion’, is proposed for the growth of HfO2 from Hf(N(CH3)2)4/H2O.1 As a second major breakthrough, a ’cooperative’ action between adsorbed precursors is shown to play an important role in ALD. By this we mean that previously-inert fragments can become reactive once sufficient molecules adsorb in their neighbourhood during either precursor pulse. As a third breakthrough, the ALD of HfO2 from Hf(N(CH3)2)4 and H2O is implemented for the first time into 3D on-lattice kinetic Monte-Carlo (KMC).2 In this integrated approach (DFT+KMC), retaining the accuracy of the atomistic model in the higher-scale model leads to remarkable breakthroughs in our understanding. The resulting atomistic model allows direct comparison with experimental techniques such as X-ray photoelectron spectroscopy and quartz crystal microbalance.

Peptide interfacial biomaterials improve endothelial cell adhesion and spreading on synthetic polyglycolic acid materials.

Resorbable scaffolds such as polyglycolic acid (PGA) are employed in a number of clinical and tissue engineering applications owing to their desirable property of allowing remodeling to form native tissue over time. However, native PGA does not promote endothelial cell adhesion. Here we describe a novel treatment with hetero-bifunctional peptide linkers, termed "interfacial biomaterials" (IFBMs), which are used to alter the surface of PGA to provide appropriate biological cues. IFBMs couple an affinity peptide for the material with a biologically active peptide that promotes desired cellular responses. One such PGA affinity peptide was coupled to the integrin binding domain, Arg-Gly-Asp (RGD), to build a chemically synthesized bimodular 27 amino acid peptide that mediated interactions between PGA and integrin receptors on endothelial cells. Quartz crystal microbalance with dissipation monitoring (QCMD) was used to determine the association constant (K (A) 1 x 10(7) M(-1)) and surface thickness (~3.5 nm). Cell binding studies indicated that IFBM efficiently mediated adhesion, spreading, and cytoskeletal organization of endothelial cells on PGA in an integrin-dependent manner. We show that the IFBM peptide promotes a 200% increase in endothelial cell binding to PGA as well as 70-120% increase in cell spreading from 30 to 60 minutes after plating.

Determination of the Physical Properties of Room Temperature Ionic Liquids Using a Love Wave Device

In this work, we have shown that a 100 MHz Love wave device can be used to determine whether room temperature ionic liquids (RTILs) are Newtonian fluids and have developed a technique that allows the determination of the density-viscosity product, rho eta of a Newtonian RTIL. In addition, a test for a Newtonian response was established by relating the phase change to insertion loss change. Five concentrations of a water-miscible RTIL and seven pure RTILs were measured. The changes in phase and insertion loss were found to vary linearly with the square root of the density-viscosity product for values up to (rho eta)(1/2) similar to 10 kg m(-2) s(-1/2). The square root of the density-viscosity product was deduced from the changes in either phase or insertion loss using glycerol as a calibration liquid. In both cases, the deduced values of rho eta agree well with those measured using viscosity and density meters. Miniaturization of the device, beyond that achievable with the lower-frequency quartz crystal microbalance approach, to measure smaller volumes is possible. The ability to fabricate Love wave and other surface acoustic wave sensors using planar metallization technologies gives potential for future integration into lab-on-a-chip analytical systems for characterizing ionic liquids.

Barrier properties of poly(lactic acid) based films

In recent years, the search for a environmentally friendly products has increased. One of the major challenges has been the demand for biodegradable materials that can replace plastic. If a few decades ago, plastic replaced, for example, the ivory in billiard balls, and in other products, saving the lives of thousands elephants, nowadays a replacement for that plastic is being searched, to prevent the change of the environmental conditions, essential to life in harmonly with the fauna and flora that the human specie has, in recent years, destroyed. Plastic is a petroleum derivate, whose price has been growing exponentially, mainly due to the fact of beind a cheap material and also to enable the production of products that are essential to modern life. Therefore, the petrochemical era is going to come to an end and a new environmentally sustainable era, based on biodegradable materials from renewable sources, will follow. The change to green routes only will be possible with the support of the major companies, and the implementation of drastic governmental law. Poly(lactic acid), PLA, is produced from the lactose present in the corn or sugarcane and has been intensively studied in recent years because if some limitants properties required its extrusion are overcome, it has the potential to replace the traditional polymers. PLA have high brittleness, low toughness and low tensile elongation. In this work, natural antioxidant (alpha-tocopherol) and synthetics antioxidants (BHT ant TBHQ) were added to the PLA with the aim not only to improve their flexibility, but also to create an active packaging to extend the shelf life of the foods and improve the organoleptic properties by preventing food losses. The impact of the addition of antioxidants into the PLA films, in its mechanical, thermal and barrier properties were studied by FTIR, DSC, SEM, AFM, DMA, TGA, QCM and time-lag techniques.

Estudo da aplicabilidade de biossensores piezoelécticos para a detecção de lipopolissacáridos bacterianos

Dissertação de Mestrado, Engenharia Biológica, Faculdade de Engenharia de Recursos Naturais, Universidade do Algarve, 2009

Development of new technologies for the selective removal of volatile compounds with applications in forensic science and natural aromas

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2015

Reference clock design for low power and low phase noise with temperature compensation

Thesis (Ph.D.)--University of Washington, 2016-03

Disposable immunosensor using a simple method for oriented antibody immobilization for label-free real-time detection of an oxidative stress biomarker implicated in cancer diseases

This work proposes a novel approach for a suitable orientation of antibodies (Ab) on an immunosensing platform, applied here to the determination of 8-hydroxy-2′-deoxyguanosine (8OHdG), a biomarker of oxidative stress that has been associated to chronic diseases, such as cancer. The anti-8OHdG was bound to an amine modified gold support through its Fc region after activation of its carboxylic functions. Non-oriented approaches of Ab binding to the platform were tested in parallel, in order to show that the presented methodology favored Ab/Ag affinity and immunodetection of the antigen. The immunosensor design was evaluated by quartz-crystal microbalance with dissipation, atomic force microscopy, electrochemical impedance spectroscopy (EIS) and square-wave voltammetry. EIS was also a suitable technique to follow the analytical behavior of the device against 8OHdG. The affinity binding between 8OHdG and the antibody immobilized in the gold modified platform increased the charge transfer resistance across the electrochemical set-up. The observed behavior was linear from 0.02 to 7.0 ng/mL of 8OHdG concentrations. The interference from glucose, urea and creatinine was found negligible. An attempt of application to synthetic samples was also successfully conducted. Overall, the presented approach enabled the production of suitably oriented Abs over a gold platform by means of a much simpler process than other oriented-Ab binding approaches described in the literature, as far as we know, and was successful in terms of analytical features and sample application.