Calibration of etched fiber bragg grating sensor arrays for measurement of molecular surface adsorption

Etched Fiber Bragg Grating (EFBG) sensors are attractive from the point of the inherently high multiplexing ability of fiber based sensors. However, the strong dependence of the sensitivity of EFBG sensors on the fiber diameter requires robust methods for calibration when used for distributed sensing in a large array format. Using experimental data and numerical modelling, we show that knowledge of the wavelength shift during the etch process is necessary for high-fidelity calibration of EFBG arrays. However as this approach requires the monitoring of every element of the sensor array during etching, we also proposed and demonstrated a calibration scheme using data from bulk refractometry measurements conducted post-fabrication without needing any information about the etching process. Although this approach is not as precise as the first one, it may be more practical as there is no requirement to monitor each element of the sensor array. We were able to calibrate the response of the sensors to within 3% with the approach using information acquired during etching and to within 5% using the post-fabrication bulk refractometry approach in spite of the sensitivities of the array element differing by more than a factor of 4. These two approaches present a tradeoff between accuracy and practicality.

The surface chemistry of nanocrystalline MgO catalysts for FAME production:an in situ XPS study of H2O, CH3OH and CH3OAc adsorption

An in situ XPS study of water, methanol and methyl acetate adsorption over as-synthesised and calcined MgO nanocatalysts is reported with a view to gaining insight into the surface adsorption of key components relevant to fatty acid methyl esters (biodiesel) production during the transesterification of triglycerides with methanol. High temperature calcined NanoMgO-700 adsorbed all three species more readily than the parent material due to the higher density of electron-rich (111) and (110) facets exposed over the larger crystallites. Water and methanol chemisorb over the NanoMgO-700 through the conversion of surface O2 − sites to OH− and coincident creation of Mg-OH or Mg-OCH3 moieties respectively. A model is proposed in which the dissociative chemisorption of methanol occurs preferentially over defect and edge sites of NanoMgO-700, with higher methanol coverages resulting in physisorption over weakly basic (100) facets. Methyl acetate undergoes more complex surface chemistry over NanoMgO-700, with C–H dissociation and ester cleavage forming surface hydroxyl and acetate species even at extremely low coverages, indicative of preferential adsorption at defects. Comparison of C 1s spectra with spent catalysts from tributyrin transesterification suggest that ester hydrolysis plays a key factor in the deactivation of MgO catalysts for biodiesel production.

Affinity adsorption of plasmid DNA

The development of a protein-mediated dual functional affinity adsorption of plasmid DNA is described in this work. The affinity ligand for the plasmid DNA comprises a fusion protein with glutathione-S-transferase (GST) as the fusion partner with a zinc finger protein. The protein ligand is first bound to the adsorbent by affinity interaction between the GST moeity and gluthathione that is covalently immobilized to the base matrix. The plasmid binding is then enabled via the zinc finger protein and a specific nucleotide sequence inserted into the DNA. At lower loadings, the binding of the DNA onto the Fractogel, Sepharose, and Streamline matrices was 0.0078 ± 0.0013, 0.0095 ± 0.0016, and 0.0080 ± 0.0006 mg, respectively, to 50 μL of adsorbent. At a higher DNA challenge, the corresponding amounts were 0.0179 ± 0.0043, 0.0219 ± 0.0035, and 0.0190 ± 0.0041 mg, respectively. The relatively constant amounts bound to the three adsorbents indicated that the large DNA molecule was unable to utilize the available zinc finger sites that were located in the internal pores and binding was largely a surface adsorption phenomenon. Utilization of the zinc finger binding sites was shown to be highest for the Fractogel adsorbent. The adsorbed material was eluted with reduced glutathione, and the eluted efficiency for the DNA was between 23% and 27%. The protein elution profile appeared to match the adsorption profiles with significantly higher recoveries of bound GST-zinc finger protein.

Effects of 9-cyanoanthracene and anthracene adsorption on the photoluminescence of porous silicon

The photoluminescence of porous silicon can be modified sensitively by surface adsorption of different kinds of molecules. A quite different effects of 9-cyanoanthracene and anthracene adsorption on the photoluminescence of porous silicon were observed. The adsorption of 9-cyanoanthracene induced the photoluminescence enhancement, while anthracene adsorption resulted in photoluminescent quenching. An explanation of the interaction of adsorbates with surface defect sites of porous silicon was suggested and discussed. (C) 1998 Elsevier Science S.A.

Adsorption and interaction of H2S/SO2 on TiO2

Adsorption and interaction of H2S/SO2 on titania as well as on alumina for comparison has been studied by temperature programmed desorption (TPD), infrared (IR) spectroscopy and temperature programmed electronic conductivity (TPEC) techniques. It was found that the adsorption of both H2S acid SO2 on TiO2 is much greater than on Al2O3. The electronic conductivity of TiO2 measured by TPEC varies significantly as adsorption and desorption takes place on TiO2, showing a strong interaction between TiO2 and adsorbates. At temperature above 200 degrees C, H2S or SO2 adsorbed on TiO2 can be converted into S, H2O and SO2 or SO3. While on the hydrogen treated TiO2, H2S is decomposed into S and H-2, SO2 into S. The active sites on TiO2 surface cannot be so strongly adsorbed by SO2 that it is much more resistant to the sulfation reaction. Unlike TiO2, Al2O3 only provides surface adsorption sites, which can be readily sulfated. The data obtained support one's understanding why TiO2 exhibits a better catalytic performance than that of Al2O3 as a Claus reaction catalyst. (C) 1999 Elsevier Science B.V. All rights reserved.

Processes influencing surface interaction and photocatalytic destruction of microcystins on titanium dioxide photocatalysts

Microcystins are a family of hepatotoxic peptides produced by freshwater cyanobacteria. Their occurrence in drinking water is of concern since chronic exposure to these toxins causes tumor promotion. It is therefore essential to establish a reliable treatment strategy that will ensure their removal from potable water. We have previously described the rapid destruction of microcystin-LR using TiO₂ photocatalysis, however, since there are at least 70 microcystin variants it is essential that the destruction of a number of microcystins be evaluated. In this study the dark adsorption and destruction of four microcystins was followed over a range of pH. All four microcystins were destroyed although the efficiency of their removal varied. The two more hydrophobic microcystins (-LW and -LF) were found to have high dark adsorption (98 and 91% at pH 4) in contrast to microcystin-RR, which was found to have almost no (only 2-3%) dark adsorption across all pH. 

Binding of pentagalloyl glucose to two globular proteins occurs via multiple surface sites

The interaction between pentagalloyl glucose (PGG) and two globular proteins, bovine serum albumin (BSA) and ribulose-1,5-bisphosphate carboxylase oxygenase (rubisco), was investigated by isothermal titration calorimetry (ITC). ITC data fit to a binding model consisting of two sets of multiple binding sites, which reveal similarities in the mode of binding of PGG to BSA and rubisco. In both cases, the interaction is characterized by a high number of binding sites, which suggests that binding occurs by a surface adsorption mechanism that leads to coating of the protein surface, which promotes aggregation and precipitation of the PGG-protein complex. This model was confirmed by turbidimetry analysis of the PGG-BSA interaction. Analysis of tryptophan fluorescence quenching during the interaction of PGG with BSA suggests that binding of PGG leads to some conformational changes that are energetically closer to the unfolded state of the BSA structure, because small red shifts in the resulting emission spectra were observed.

Adsorption of anionic amphiphilic polyelectrolytes onto amino-terminated solid surfaces

The adsorption behavior of several amphiphilic polyelectrolytes of poly(maleic anhydride-alt-styrene) functionalized with naphthyl and phenyl groups, onto amino-terminated silicon wafer has been studied by means of null- ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The maximum of adsorption, Gamma(plateau), varies with the ionic strength, the polyelectrolyte structure and the chain length. Values of Gamma(plateau) obtained at low and high ionic strengths indicate that the adsorption follows the ""screening-reduced adsorption"" regime. Large aggregates were detected in solution by means of dynamic light scattering and fluorescence measurements. However. AFM indicated the formation of smooth layers and the absence of aggregates. A model based on a two-step adsorption behavior was proposed. In the first one, isolated chains in equilibrium with the aggregates in solution adsorbed onto amino-terminated surface. The adsorption is driven by electrostatic interaction between protonated surface and carboxylate groups. This first layer exposes naphtyl or phenyl groups to the solution. The second layer adsorption is now driven by hydrophobic interaction between surface and chains and exposes carboxylate groups to the medium, which repel the forthcoming chain by electrostatic repulsion. Upon drying some hydrophobic naphtyl or phenyl groups might be oriented to the air, as revealed by contact angle measurements. Such amphiphilic polyelectrolyte layers worked well for the building-up of multilayers with chitosan. (C) 2010 Elsevier Ltd. All rights reserved.

The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

In order to evaluate the interactions between Au/Cu atoms and clean Si(l 11) surface, we used synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations. Optimized geometries and energies on different adsorption sites indicate that the binding energies at different adsorption sites are high, suggesting a strong interaction between metal atom and silicon surface. The Au atom showed higher interaction than Cu atom. The theoretical and experimental data showed good agreement. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Inverted critical adsorption of polyelectrolytes in confinement

What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer-surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density sigma(c)-defining the adsorption-desorption transition-are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of sigma(c) for the concave interfaces versus the Debye screening length 1/kappa and the extent of confinement a for these three interfaces for small kappa a values. For large kappa a the critical adsorption condition approaches the known planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness a is of the order of 1/kappa. We also rationalize how sigma(c)(kappa) dependence gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length for critical adsorption-the effect often hard to tackle theoretically-putting an emphasis on polymers inside attractive spherical cavities. The applications of our findings to some biological systems are discussed, for instance the adsorption of nucleic acids onto the inner surfaces of cylindrical and spherical viral capsids.

Interactions between 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and gamma-Al2O3 (100) surface calculated by density functional theory

The main aim of this work is to investigate the 1-butyl-3-methylimidazolium tetrafluoroborate ([C4C1Im]+[BF4]-) ionic liquid (IL) adsorption on the gamma-Al2O3 (100) by density functional theory calculations to try to rationalize the adsorption as an electrostatic phenomenon. Optimized geometries and interaction energies of IL one-monolayer on the gamma-Al2O3 were obtained on high surface coverage (one cationanion pair per 94.96 nm2). A study of dispersion force was made to estimate its contribution to the adsorption. Overall, the process is ruled by electrostatic interaction between ions and surface. Adsorption of the anion [BF4]- and cation [C4C1Im]+ was also studied by Bader charge analysis and charge density difference for supported and unsupported situations. It is suggested that the IL ions have their charges maintained with significant anion cloud polarization inward to the acid aluminum sites. (c) 2012 Wiley Periodicals, Inc.

Computational modeling of surface interactions

Die Wechselwirkung zwischen Proteinen und anorganischen Oberflächen fasziniert sowohl aus angewandter als auch theoretischer Sicht. Sie ist ein wichtiger Aspekt in vielen Anwendungen, unter anderem in chirugischen Implantaten oder Biosensoren. Sie ist außerdem ein Beispiel für theoretische Fragestellungen betreffend die Grenzfläche zwischen harter und weicher Materie. Fest steht, dass Kenntnis der beteiligten Mechanismen erforderlich ist um die Wechselwirkung zwischen Proteinen und Oberflächen zu verstehen, vorherzusagen und zu optimieren. Aktuelle Fortschritte im experimentellen Forschungsbereich ermöglichen die Untersuchung der direkten Peptid-Metall-Bindung. Dadurch ist die Erforschung der theoretischen Grundlagen weiter ins Blickfeld aktueller Forschung gerückt. Eine Möglichkeit die Wechselwirkung zwischen Proteinen und anorganischen Oberflächen zu erforschen ist durch Computersimulationen. Obwohl Simulationen von Metalloberflächen oder Proteinen als Einzelsysteme schon länger verbreitet sind, bringt die Simulation einer Kombination beider Systeme neue Schwierigkeiten mit sich. Diese zu überwinden erfordert ein Mehrskalen-Verfahren: Während Proteine als biologische Systeme ausreichend mit klassischer Molekulardynamik beschrieben werden können, bedarf die Beschreibung delokalisierter Elektronen metallischer Systeme eine quantenmechanische Formulierung. Die wichtigste Voraussetzung eines Mehrskalen-Verfahrens ist eine Übereinstimmung der Simulationen auf den verschiedenen Skalen. In dieser Arbeit wird dies durch die Verknüpfung von Simulationen alternierender Skalen erreicht. Diese Arbeit beginnt mit der Untersuchung der Thermodynamik der Benzol-Hydratation mittels klassischer Molekulardynamik. Dann wird die Wechselwirkung zwischen Wasser und den [111]-Metalloberflächen von Gold und Nickel mittels eines Multiskalen-Verfahrens modelliert. In einem weiteren Schritt wird die Adsorbtion des Benzols an Metalloberflächen in wässriger Umgebung studiert. Abschließend wird die Modellierung erweitert und auch die Aminosäuren Alanin und Phenylalanin einbezogen. Dies eröffnet die Möglichkeit realistische Protein- Metall-Systeme in Computersimulationen zu betrachten und auf theoretischer Basis die Wechselwirkung zwischen Peptiden und Oberflächen für jede Art Peptide und Oberfläche vorauszusagen.

The visualisation of vitreous using surface modified poly(lactic-co-glycolic acid) microparticles

AIMS To demonstrate the potential use of in vitro poly(lactic-co-glycolic acid) (PLGA) microparticles in comparison with triamcinolone suspension to aid visualisation of vitreous during anterior and posterior vitrectomy. METHODS PLGA microparticles (diameter 10-60 microm) were fabricated using single and/or double emulsion technique(s) and used untreated or following the surface adsorption of a protein (transglutaminase). Particle size, shape, morphology and surface topography were assessed using scanning electron microscopy (SEM) and compared with a standard triamcinolone suspension. The efficacy of these microparticles to enhance visualisation of vitreous against the triamcinolone suspension was assessed using an in vitro set-up exploiting porcine vitreous. RESULTS Unmodified PLGA microparticles failed to adequately adhere to porcine vitreous and were readily washed out by irrigation. In contrast, modified transglutaminase-coated PLGA microparticles demonstrated a significant improvement in adhesiveness and were comparable to a triamcinolone suspension in their ability to enhance the visualisation of vitreous. This adhesive behaviour also demonstrated selectivity by not binding to the corneal endothelium. CONCLUSION The use of transglutaminase-modified biodegradable PLGA microparticles represents a novel method of visualising vitreous and aiding vitrectomy. This method may provide a distinct alternative for the visualisation of vitreous whilst eliminating the pharmacological effects of triamcinolone acetonide suspension.

Vertically-aligned carbon nanotube membranes for hydrogen separation

Vertically-aligned carbon nanotube membranes have been fabricated and characterized and the corresponding gas permeability and hydrogen separation were measured. The carbon nanotube diameter and areal density were adjusted by varying the catalyst vapour concentration (Fe/C ratio) in the mixed precursor. The permeances are one to two magnitudes higher than the Knudsen prediction, while the gas selectivities are still in the Knudsen range. The diameter and areal density effects were studied and compared, the temperature dependence of permeation is also discussed. The results confirm the existence of non-Knudsen transport and that surface adsorption diffusion may affect the total permeance at relative low temperature. The permeance of aligned carbon nanotube membranes can be improved by increasing areal density and operating at an optimum temperature.