Smart Plastic Antibody Material for Hemoglobin Tailored by Silica Surface Imprinting and with Charged Binding Sites: Its use as Ionophore in Potentiometric Transduction

JORNADAS DE ELECTROQUÍMICA E INOVAÇÃO 2013

Surface acidity and catalytic activity of sulphated samaria

We have investigated the changes in surface acidity/basicity and catalytic pro~erties of samarium oxide due to surface modification by SO42- ion. The acidity/basicity of the catalysts is determined by titration method using Hammett indicators. Esterification of acetic acid by n-butanol is chosen as a test reaction. Sm203, owing to its high basicity and low acidity, does not catalyze the reaction. But sulphated Sm20J catalyzes the esterification reaction effectively. Activation temperature does not have much effect on the acidity of sulphated samaria.

Modification and Analysis of Group-13-Nitride Semiconductor Surfaces: Influence of Adsorbates on Device Characteristics and Processing

Im Rahmen dieser interdisziplinären Doktorarbeit wird eine (Al)GaN Halbleiteroberflächenmodifikation untersucht, mit dem Ziel eine verbesserte Grenzfläche zwischen dem Material und dem Dielektrikum zu erzeugen. Aufgrund von Oberflächenzuständen zeigen GaN basierte HEMT Strukturen üblicherweise große Einsatzspannungsverschiebungen. Bisher wurden zur Grenzflächenmodifikation besonders die Entfernung von Verunreinigungen wie Sauerstoff oder Kohlenstoff analysiert. Die nasschemischen Oberflächenbehandlungen werden vor der Abscheidung des Dielektrikums durchgeführt, wobei die Kontaminationen jedoch nicht vollständig entfernt werden können. In dieser Arbeit werden Modifikationen der Oberfläche in wässrigen Lösungen, in Gasen sowie in Plasma analysiert. Detaillierte Untersuchungen zeigen, dass die inerte (0001) c-Ebene der Oberfläche kaum reagiert, sondern hauptsächlich die weniger polaren r- und m- Ebenen. Dies kann deutlich beim Defektätzen sowie bei der thermischen Oxidation beobachtet werden. Einen weiteren Ansatz zur Oberflächenmodifikation stellen Plasmabehandlungen dar. Hierbei wird die Oberflächenterminierung durch eine nukleophile Substitution mit Lewis Basen, wie Fluorid, Chlorid oder Oxid verändert, wodurch sich die Elektronegativitätsdifferenz zwischen dem Metall und dem Anion im Vergleich zur Metall-Stickstoff Bindung erhöht. Dies führt gleichzeitig zu einer Erhöhung der Potentialdifferenz des Schottky Kontakts. Sauerstoff oder Fluor besitzen die nötige thermische Stabilität um während einer Silicium-nitridabscheidung an der (Al)GaN Oberfläche zu bleiben. Sauerstoffvariationen an der Oberfläche werden in NH3 bei 700°C, welches die nötigen Bedingungen für die Abscheidung darstellen, immer zu etwa 6-8% reduziert – solche Grenzflächen zeigen deswegen auch keine veränderten Ergebnisse in Einsatzspannungsuntersuchungen. Im Gegensatz dazu zeigt die fluorierte Oberfläche ein völlig neues elektrisches Verhalten: ein neuer dominanter Oberflächendonator mit einem schnellen Trapping und Detrapping Verhalten wird gefunden. Das Energieniveau dieses neuen, stabilen Donators liegt um ca. 0,5 eV tiefer in der Bandlücke als die ursprünglichen Energieniveaus der Oberflächenzustände. Physikalisch-chemische Oberflächen- und Grenzflächenuntersuchung mit XPS, AES oder SIMS erlauben keine eindeutige Schlussfolgerung, ob das Fluor nach der Si3N4 Abscheidung tatsächlich noch an der Grenzfläche vorhanden ist, oder einfach eine stabilere Oberflächenrekonstruktion induziert wurde, bei welcher es selbst nicht beteiligt ist. In beiden Fällen ist der neue Donator in einer Konzentration von 4x1013 at/cm-2 vorhanden. Diese Dichte entspricht einer Oberflächenkonzentration von etwa 1%, was genau an der Nachweisgrenze der spektroskopischen Methoden liegt. Jedoch werden die elektrischen Oberflächeneigenschaften durch die Oberflächenmodifikation deutlich verändert und ermöglichen eine potentiell weiter optimierbare Grenzfläche.

Heterogeneously catalyzed asymmetric hydrogenation of C = C bonds directed by surface-tethered chiral modifiers

Asymmetric hydrogenation of C=C bonds is of the highest importance in organic synthesis, and such reactions are currently carried out with organometallic homogeneous catalysts. Achieving heterogeneous metal-catalyzed hydrogenation, a highly desirable goal, necessitates forcing the crucial enantiodifferentiating step to take place at the metal surface. By synthesis and application of six chiral sulfide ligands that anchor robustly to Pd nanoparticles and resist displacement, we have for the first time accomplished heterogeneous enantioselective catalytic hydrogenation of isophorone. High resolution XPS data established that ligand adsorption from solution occurred exclusively on the Pd nanoparticles and not on the carbon support. All ligands contained a pyrrolidine nitrogen to enable their interaction with the isophorone substrate while the sulfide functionality provided the required interaction with the Pd surface. Enantioselective turnover numbers of up to similar to 100 product molecules per ligand molecule were found with a very large variation in asymmetric induction between ligands: observed enantiomeric excesses increased with increasing size of the alkyl group in the sulfide. This likely reflects varying degrees of ligand dispersion on the surface: bulky substituent groups hinder close approach of ligand molecules to each other, inhibiting close-packed island formation, favoring dispersion as separate molecules, and leading to effective asymmetric induction. Conversely, small substituents favor island formation leading to very low asymmetric induction. Enantioselective reaction most likely involves initial formation of an enamine or iminium species, confirmed by use of an analogous tertiary amine, which leads to racemic product. Ligand rigidity and resistance to self-assembled monolayer formation are important attributes that should be designed into improved chiral modifiers.

Model car-exhaust catalyst studied by TPD and TP-RAIRS: Surface reactions of NO on clean and O-covered Ir{100}

The adsorption of NO on Ir{100} has been studied as a function of NO coverage and temperature using temperature programmed reflection absorption infrared spectroscopy (TP-RAIRS), low energy electron diffraction (LEED) and temperature programmed desorption (TPD). After saturating the clean (1 x 5)-reconstructed surface with NO at 95 K. two N-2, desorption peaks are observed upon heating. The first N-2 peak at 346 K results from the decomposition of bridge-bonded NO, and the second at 475 K from the decomposition of atop-bonded NO molecules. NO decomposition is proposed to be the rate limiting step for both N-2 desorption states. For high NO coverages on the (1 x 5) surface, the narrow width of the first N-2 desorption peak is indicative of an autocatalytic process for which the parallel formation of N2O appears to be the crucial step. When NO is adsorbed on the metastable unreconstructed (1 x 1) phase of clean Ir{100} N-2 desorption starts at lower temperatures, indicating that this surface modification is more reactive. When a high coverage of oxygen, near 0.5 ML, is pre-adsorbed on the surface, the decomposition of NO is inhibited and mainly desorption of intact NO is observed.

Aggregation, ageing and transport properties of surface modified fumed silica dispersions

We have investigated the aggregation, ageing and transport properties of surface modified silica dispersions in DMSO by photon correlation spectroscopy and conductivity measurements. The surface modification introduces Li+-ions that dissociate in the dispersion creating a single Li+-ion conducting electrolyte. We show that the surface modification changes the aggregation and ageing properties of the material. There is a pronounced ageing observed for the modified silica dispersions. At high concentrations of fumed silica a gel state is found, which in the case of the surface modified silica is a very weak gel that can be rejuvenated by ultrasonic treatment. The key parameter controlling the aggregation in this system is hydrogen bonding and the surface modification results in a very low number of sites for hydrogen bonding. In addition there is a contribution from repulsive electrostatic interactions in the surface modified silica dispersions due to the highly charged surfaces of these particles. Furthermore, the Li+-ion diffusion, at low silica concentration, is three orders of magnitude faster than that of the silica particles and in the gel state the silica particles are immobile. We also find that the Li+-ion diffusion is virtually independent of the silica concentration in the dispersions.

Exploring molecular changes at the surface of polypropylene after accelerated thermomolecular adhesion treatments

A central composite rotatable design (CCRD) method was used to investigate the performance of the accelerated thermomolecular adhesion process (ATmaP), at different operating conditions. ATmaP is a modified flame-treatment process that features the injection of a coupling agent into the flame to impart a tailored molecular surface chemistry on the work piece. In this study, the surface properties of treated polypropylene were evaluated using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). All samples showed a significant increase in the relative concentration of oxygen (up to 12.2%) and nitrogen (up to 2.4%) at the surface in comparison with the untreated sample (0.7% oxygen and no detectable nitrogen) as measured by XPS. ToF-SIMS and principal components analysis (PCA) showed that ATmaP induced multiple reactions at the polypropylene surface such as chain scission, oxidation, nitration, condensation, and molecular loss, as indicated by changes in the relative intensities of the hydrocarbon (C₃H₇⁺ , C₃H₅⁺ , C₄H₇⁺, and C₅H₉⁺), nitrogen and oxygen-containing secondary ions (C₂H₃O⁺, C₃H₈N⁺, C₂H₅NO⁺, C₃H₆NO⁺, and C₃H₇NO⁺). The increase in relative intensity of the nitrogen oxide ions (C₂H₅NO⁺ and C₃H₇NO⁺) correlates with the process of incorporating oxides of nitrogen into the surface as a result of the injection of the ATmaP coupling agent.

Tailoring the surface chemistry of carbon fiber and E-glass composites for improved adhesion

The main challenges in the manufacture of composite materials are low surface energy and the presence of silicon-containing contaminants, both of which greatly reduce surface adhesive strength. In this study, carbon fiber (CF) and E-glass epoxy resin composites were surface treated with the Accelerated Thermo-molecular adhesion Process (ATmaP). ATmaP is a multiaction surface treatment process where tailored nitrogen and oxygen functionalities are generated on the surface of the sample through the vaporization and atomization of n-methylpyrrolidone solution, injected via specially designed flame-treatment equipment. The treated surfaces of the polymer composites were analyzed using XPS, time of flight secondary ion mass spectrometry (ToF-SIMS), contact angle (CA) analysis and direct adhesion measurements. ATmaP treatment increased the surface concentration of polar functional groups while reducing surface contamination, resulting in increased adhesion strength. XPS and ToF-SIMS showed a significant decrease in silicon-containing species on the surface after ATmaP treatment. E-glass composite showed higher adhesion strength than CF composite, correlating with higher surface energy, higher concentrations of nitrogen and CO functional groups (from XPS) and higher concentrations of oxygen and nitrogen-containing functional groups (particularly C₂H₃O⁺ and C₂H₅NO⁺ molecular ions, from ToF-SIMS).

In vitro behavior of human osteoblast-like cells (SaOS2) cultured on surface modified titanium and titanium–zirconium alloy

In this study, titanium (Ti) and titanium-zirconium (TiZr) alloy samples fabricated through powder metallurgy were surface modified by alkali-heat treatment and calcium (Ca)-ion-deposition. The alteration of the surface morphology and the chemistry of the Ti and TiZr after surface modification were examined. The bioactivity of the Ti and TiZr alloys after the surface modification was demonstrated. Subsequently, the cytocompatibility of the surface modified Ti and TiZr was evaluated via in vitro cell culture using human osteoblast-like cells (SaOS2). The cellular attachment, adhesion and proliferation after cell culture for 14 days were characterized by scanning electron microscopy (SEM) and MTT assay. The relationship between surface morphology and chemical composition of the surface modified Ti and TiZr and cellular responses was investigated. Results indicated that the surface-modified Ti and TiZr alloys exhibited excellent in vitro cytocompatibility together with satisfactory bioactivity. Since osteoblast adhesion and proliferation are essential prerequisites for a successful implant in vivo, these results provide evidence that Ti and TiZr alloys after appropriate surface modification are promising biomaterials for hard tissue replacement.

Chemical and thermal stability of surface‐modified porous polyethylene membranes

In this paper, we describe the surface modification of porous polyethylene by the adsorption of polyelectrolyte mutilayers on plasma‐activated polyethylene surfaces. We use the migration rates of deionized water as an effective alternative to contact angle measurements in order to probe the interfacial energy of the modified surface. The newly acquired surface properties that result from the surface modification are monitored with respect to several key chemical and environmental variables. These variables were chosen so that they will reflect some of the common handling procedures in a laboratory or health care environments, such as exposure to solvents of different pH and polarities, and fluctuations of ambient temperature over an extended period, i.e., “shelf‐life” duration. The stability of these surface properties of the modified membranes is a fundamental requirement for their potential use in a variety of applications involving lateral flow and binding media for bio‐assays. In this paper, we show that a membrane modified by a polyelectrolyte monolayer is more stable than a membrane that has undergone plasma activation alone, while a membrane modified by a polyelectrolyte bilayer exhibits retention of the enhanced surface hydrophilic properties under various conditions and over a long period of time.

Effect of surface treatment and knit structure on comfort properties of wool fabrics

The comfort properties of the pique and single jersey knitted wool fabrics were investigated using the Wool ComfortMeter (WCM). The fabrics were knitted in three cover factors and treated with either plasma or a silicone softening agent and were compared with untreated fabrics. Plasma treatment did not show significant effects on the comfort value. However, silicone polymer significantly reduced WCM values suggesting that the silicone coating reduced the number of protruding fibres on the fabric surface. Regardless of treatment used, pique fabrics showed a lower WCM value, and therefore were perceived to be more comfortable than the single jersey structure. While the effect of cover factor was not significant, in fitted model to predict the WCM value of fabrics, mass/unit area and fabric thickness were significant predictors along with fabric structure and finishing treatment.

Surface functionalisation of magnesium alloys for use as bio-implants

 Magnesium-based alloys containing appropriate quantities of Strontium can induce optimal bone formation. Surface modification of these alloys with Collagen-I increased mineral deposition on the peri-implant surface over shorter periods of time as compared to the unmodified alloys, indicating the role of Collagen-I and Strontium concentration in bone resorption and remodelling.

Use of Saponins as an Effective Surface Modifier in Cellulose Nanocomposites

The present paper deals with the extraction of saponins from the pericarp of Sapindus mukorossi to use as compatibilizer in nanocomposites. The nanofibrils extracted from banana fibres are utilized as reinforcement of nanocomposite. These nanofibers were treated with Saponin, GPS (3-Glycidoxypropyltrimethoxysilane) and APS (3-Aminopropyltriethoxysilane) to compare the effectiveness of surface treatment. The effectiveness of surface modification was reflected on the increase in mechanical (tensile test, flexural modulus, impact test) properties and decrease in the RMS (Roughness Measurement System) roughness investigation by SFM (Scanning force microscopy) analysis.