Dissolution kinetics of octadecanethiolate monolayers electro-adsorbed on Au(1 1 1)

Monolayers of octadecanethiolate on Au(1 1 1) surface were formed under electrochemical control. The influence of the formation time on the reductive desorption process was studied by cyclic voltammetry and chronoamperometry. When the formation time is increased, the reductive desorption peak observed on the voltammograms is significantly shifted in the negative direction, while the cathodic charge is only slightly affected. This behaviour is attributed to a higher degree of organisation of the monolayers for longer formation times, highlighting the role of defect sites in promoting the dissolution. A good agreement was found between our experimental chronoamperograms and theoretical models describing the dissolution process by a shrinkage mechanism. It is demonstrated that a reorganisation process takes place, consisting in the merging of small condensed domains into larger ones. This annealing phenomenon is time and potential dependent, the largest condensed domains being obtained for the longest formation times and least negative potentials. © 2008 Elsevier B.V. All rights reserved.

Mixed self-assembled monolayers of 2-mercaptobenzimidazole and 2-mercaptobenzimidazole-5-sulfonate: determination and control of the surface composition

The behaviour towards electron transfer of self-assembled monolayers of 2-mercaptobenzimidazole (MBI) and 2-mercaptobenzimidazole-5-sulfonate (MBIS) on Au(1 1 1) was examined by cyclic voltammetry. The influence of the monolayers was drastically dependent on the charge of the redox probe used. When [Ru(NH3)6]3+ is used, a post-adsorption peak characteristic of the adsorption of the redox probe is detected only at the MBIS modified electrode. Taking advantage of this difference, ac voltammetry has been used to determine the surface composition when mixed monolayers are formed by immersion of the gold substrate in mixtures of different molar fractions of MBI and MBIS. Results clearly indicate that the ionic strength of the immersion solution plays a key role in the surface composition when a charged surfactant is mixed with non-charged surfactant. © 2006 Elsevier B.V. All rights reserved.

On the adsorption of hexaammineruthenium (III) at anionic self-assembled monolayers

The binding of the electroactive hexaammineruthenium (III) complex ions to anionic self-assembled monolayers (SAMs) has been investigated by means of chronocoulometry and ac voltammetry. From chronocoulometric data recorded in 10-2 M LiClO4 containing different [Ru(NH3)6]3+ concentrations, we have established the adsorption isotherm of [Ru(NH3)6]3+ on a compact monolayer of 2-mercaptobenzimidazole-5-sulfonate (MBIS) self-assembled on Au(1 1 1). The data were satisfactorily fitted to the linearized Langmuir adsorption isotherm and a binding constant of 4.0 (±0.4) × 106 M-1 has been determined. The electrostatic binding of [Ru(NH3)6]3+ to a dilute PNA-DNA monolayer formed after hybridization on a PNA-modified gold electrode by self-assembly from a mixed solution of mercaptobutan-1-ol and PNA oligonucleotides has been studied by ac voltammetry. The admittance of the PNA-modified electrode after hybridization with complementary DNA was measured in 0.01 M Tris-HCl buffer containing different [Ru(NH3)6]3+ concentrations. Based on these data, a binding constant of [Ru(NH3)6]3+ to the surface-confined PNA-DNA duplex was derived from the Langmuir isotherm and amounts to 2.9 (±0.3) × 105 M-1. As the interactions between [Ru(NH3)6]3+ and the immobilized PNA-DNA hybrids on the gold surface are essentially electrostatic, the adsorption of the highly charged cationic redox complex at low concentrations to the negatively charged PNA-DNA modified surface is in large competition with other monovalent cations present in the electrolyte at higher concentrations. The influence of competing sodium cations was thus studied by adding different NaCl concentrations in the 0.01 M Tris-HCl electrolyte. © 2008 Elsevier Ltd. All rights reserved.

A novel syndrome of severe neutrophil dysfunction: unresponsiveness confined to chemotaxin-induced functions.

We have identified a patient with a number of neutrophil dysfunctions. The patient was a female baby who lived for 8 months. During her life, she developed severe bacterial infections and showed omphalitis, impaired wound healing, and a pronounced leukocytosis. She was not a patient with leukocyte adhesion deficiency, because all leukocyte CD18 complex proteins were expressed at normal levels. Yet, neutrophil polarization and chemotaxis to platelet-activating factor, leukotriene B4, or formyl-methionyl-leucyl-phenylalanine (FMLP) were completely absent. We found a strong defect in actin polymerization in response to chemotactic stimuli, but only a retarded or even normal reaction with other stimuli. This indicates that the cellular dysfunctions were not due to an intrinsic defect in actin metabolism. Instead, the regulation of actin polymerization with chemotactic stimuli seemed to be defective. We concentrated on FMLP-induced responses in the patient's neutrophils. Functions dependent on activation of complement receptor type 3, such as aggregation or adherence to endothelial cells, were normally induced. Binding to serum-coated coverslips was normal in cell number; however, spreading was not observed. Exocytosis from the specific granules was readily induced. In contrast, FMLP failed to induce a respiratory burst activity or degranulation of the azurophil granules. FMLP induced a normal increase in free intracellular Ca2+, but a decreased formation of diglycerides (especially the 1-O-alkyl,2-acyl compounds). Thus, we have described a patient whose neutrophils show a severe defect in functional activation via chemotaxin receptors, resulting in a selective absence of NADPH oxidase activity, exocytosis from the azurophil granules, and actin polymerization. Our findings show that actin polymerization for neutrophil spreading and locomotion is regulated differently from that for phagocytosis. Also, the release of azurophil and specific granule contents is clearly shown to be regulated in a different way.