Influence of Electrostatic Interactions between Surface Species on the Surface Reactivity of a Molecular Layer

Adsorption ◽  
2020 ◽  
Author(s):  
Karolina Szymanek ◽  
Robert Charmas ◽  
Wojciech Piasecki

Abstract Research on Ca2+ adsorption onto the mineral surface is of significant importance with regard to geochemical processes. Sverjensky (Geochim Cosmochim Acta 70(10), 2427–2453, 2006) assumed that alkaline earths form two types of surface species on oxides: tetranuclear (> SOH)2(> SO−)2_M(OH)+ and mononuclear > SO−_M(OH)+. To look into the above assumption we investigated calcium adsorption on SiO2 and Al2O3 because they are the most widespread minerals in the environment. We have determined the proton surface charge, electrokinetic potential and metal adsorption as a function of pH. The Ca2+ uptake and concentration in the system were monitored by the calcium ion-selective electrode (Ca-ISE). The Ca-ISE measurements indicated a similar affinity of Ca2+ for both materials despite their differently charged surface, negative for silica and mainly positive for alumina. This may suggest that simple electrostatic interactions are not the primary driving force for calcium adsorption, and that solvation of calcium ions at the surface may be crucial. We have analyzed our experimental data using the 2-pK triple-layer model (2-pK TLM). Three calcium complexes on the mineral surface were reported. Two of them were the same for both oxides, i.e. the tetranuclear ($$>$$ >  SOH)2($$>$$ >  SO−)2_Ca2+ and mononuclear complexes > SO−_CaOH+. Additionally, minor contribution from >SOH…Ca2+ for silica was assumed. In the case of Al2O3 the hydrolyzed tetranuclear complexes ($$>$$ >  SOH)2($$>$$ >  SO−)2_CaOH+ at pH > 7.5 occurred based on the modeling results. Two types of surface complexes suggested by Sverjensky allowed for the correct description of proton and calcium uptake for alumina. However, the electrokinetic data excluded hydrolyzed tetranuclear surface species for this oxide.


Langmuir ◽  
2006 ◽  
Vol 22 (1) ◽  
pp. 26-28 ◽  
Author(s):  
Tingji Tang ◽  
Jiangqiang Qu ◽  
Klaus Müllen ◽  
Stephen E. Webber

1992 ◽  
Vol 259 ◽  
Author(s):  
A.C. Dillon ◽  
M.B. Robinson ◽  
S.M. George ◽  
P. Gupta

ABSTRACTHydrogen passivation of silicon surfaces plays an important role in silicon surface cleaning and preparation. To measure the effect of hydrogen passivation on silicon surface reactivity, Fourier transform infrared (FTIR) transmission spectroscopy was used to monitor the oxidation of silicon surfaces versus hydrogen coverage. Experiments were performed insitu in an ultrahigh vacuum (UHV) chamber using high surface area poroussilicon samples. Si-H stretching and bending vibrations and Si-O-Si stretching vibrations were employed to monitor the silicon surface species. Oxidation studies with O2 conducted versus various initial hydrogen coverages revealed that oxidation rates and apparent oxygen saturation levels on porous silicon decreased as a function of initial surface hydrogen coverage. Exceptional surface stability was observed when the porous silicon surface was passivated by both monohydride and dihydride surface species. In addition, new blue-shifted Si-H stretching and bending features were observed following the oxidation of partially hydrogen-passivated porous silicon which indicated the presence of Ox SiH species. Thermal annealing studies revealed that the thermal stability of these OxSiH species increased with increasing oxidation of the silicon surface. These results have important implications for silicon growth and surface cleaning because they indicate that hydrogen removal is more difficult when the silicon surface is contaminated with oxygen. These FTIR results have also been compared with earlier results of oxidation versus hydrogen coverage on Si(111) 7×7.


Author(s):  
R.V.W. Dimlich ◽  
M.H. Biros

Although a previous study in this laboratory determined that Purkinje cells of the rat cerebellum did not appear to be damaged following 30 min of forebrain ischemia followed by 30 min of reperfusion, it was suggested that an increase in rough endoplasmic reticulum (RER) and/or polysomes had occurred in these cells. The primary objective of the present study was to morphometrically determine whether or not this increase had occurred. In addition, since there is substantial evidence that glial cells may be affected by ischemia earlier than other cell types, glial cells also were examined. To ascertain possible effects on other cerebellar components, granule cells and neuropil near Purkinje cells as well as neuropil in the molecular layer also were evaluated in this investigation.


Author(s):  
K. Cullen-Dockstader ◽  
E. Fifkova

Normal aging results in a pronounced spatial memory deficit associated with a rapid decay of long-term potentiation at the synapses between the perforant path and spines in the medial and distal thirds of the dentate molecular layer (DML), suggesting the alteration of synaptic transmission in the dentate fascia. While the number of dentate granule cells remains unchanged, and there are no obvious pathological changes in these cells associated with increasing age, the density of their axospinous contacts has been shown to decrease. There are indications that the presynaptic element is affected by senescence before the postsynaptic element, yet little attention has been given to the fine structure of the remaining axon terminals. Therefore, we studied the axon terminals of the perforant path in the DML across three age groups.5 Male rats (Fischer 344) of each age group (3, 24 and 30 months), were perfused through the aorta.


Author(s):  
Brigid R. Heywood ◽  
S. Champ

Recent work on the crystallisation of inorganic crystals under compressed monomolecular surfactant films has shown that two dimensional templates can be used to promote the oriented nucleation of solids. When a suitable long alkyl chain surfactant is cast on the crystallisation media a monodispersied population of crystals forms exclusively at the monolayer/solution interface. Each crystal is aligned with a specific crystallographic axis perpendicular to the plane of the monolayer suggesting that nucleation is facilitated by recognition events between the nascent inorganic solid and the organic template.For example, monolayers of the long alkyl chain surfactant, stearic acid will promote the oriented nucleation of the calcium carbonate polymorph, calcite, on the (100) face, whereas compressed monolayers of n-eicosyl sulphate will induce calcite nucleation on the (001) face, (Figure 1 & 2). An extensive program of research has confirmed the general principle that molecular recognition events at the interface (including electrostatic interactions, geometric homology, stereochemical complementarity) can be used to promote the crystal engineering process.


1998 ◽  
Vol 80 (08) ◽  
pp. 310-315 ◽  
Author(s):  
Marie-Christine Bouton ◽  
Christophe Thurieau ◽  
Marie-Claude Guillin ◽  
Martine Jandrot-Perrus

SummaryThe interaction between GPIb and thrombin promotes platelet activation elicited via the hydrolysis of the thrombin receptor and involves structures located on the segment 238-290 within the N-terminal domain of GPIbα and the positively charged exosite 1 on thrombin. We have investigated the ability of peptides derived from the 269-287 sequence of GPIbα to interact with thrombin. Three peptides were synthesized, including Ibα 269-287 and two scrambled peptides R1 and R2 which are comparable to Ibα 269-287 with regards to their content and distribution of anionic residues. However, R2 differs from both Ibα 269-287 and R1 by the shifting of one proline from a central position to the N-terminus. By chemical cross-linking, we observed the formation of a complex between 125I-Ibα 269-287 and α-thrombin that was inhibited by hirudin, the C-terminal peptide of hirudin, sodium pyrophosphate but not by heparin. The complex did not form when γ-thrombin was substituted for α-thrombin. Ibα 269-287 produced only slight changes in thrombin amidolytic activity and inhibited thrombin binding to fibrin. R1 and R2 also formed complexes with α-thrombin, modified slightly its catalytic activity and inhibited its binding to fibrin. Peptides Ibα 269-287 and R1 inhibited platelet aggregation and secretion induced by low thrombin concentrations whereas R2 was without effect. Our results indicate that Ibα 269-287 interacts with thrombin exosite 1 via mainly electrostatic interactions, which explains why the scrambled peptides also interact with exosite 1. Nevertheless, the lack of effect of R2 on thrombin-induced platelet activation suggests that proline 280 is important for thrombin interaction with GPIb.


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