Interactions of Na+, K+, Mg2+, and Ca2+ with benzene self-assembled monolayers.

Interactions between cations and organic molecules are found throughout nature, from the functionality and structure of proteins in humans and animals to the exchange of ions in minerals in soil and oil reservoirs with the fluid phases. We have explored the behavior of the s-block elements that are most common in the natural world, namely, Na(+), K(+), Mg(2+), and Ca(2+). Specifically, we investigated how these ions affect the interactions between surfaces covered by self-assembled monolayers (SAMs) terminated with benzene molecules. We used a flat oxidized silicon substrate and an atomic force microscopy (AFM) tip that were both functionalized with 11-phenoxyundecane-1-thiol and measured the adhesion force between them in solutions of each of the four chloride salts. We observed that the adhesion increased in the order of the Hofmeister series: K(+) < Na(+) ≈ Mg(2+) < Ca(2+). Supplementary evidence from X-ray photoelectron spectroscopy (XPS) allowed us to conclude that K(+) binds in the benzene layers, creating a positive surface charge on the benzene-covered surfaces, thus leading to lower adhesion in KCl solutions than in pure water. Evidence suggested that Ca(2+) does not bind to the surfaces but forms bridges between the layers, leading to higher adhesion than in pure water. In Na(+) and Mg(2+) solutions, adhesion is quite similar to that in pure water, indicating a lack of interaction between these two ions and the surfaces, or at least that the interaction is too weak to be detected by our measurements. The results of our studies clearly show that even a nonpolar, hydrophobic molecule, such as benzene, has a role to play in the behavior of aqueous solutions and that it interacts differently depending on which ions are present. Even ions from the same column in the periodic table behave differently.

Adhesion of alkane as a functional group on muscovite and quartz: dependence on pH and contact time.

The interactions between mineral surfaces and organic molecules in water control many processes in nature and in the production of modern materials. To improve the understanding of fluid-surface interactions, we investigated the interface behavior of quartz and muscovite, a model for clay minerals, in aqueous solutions where the pH and composition were controlled. We used atomic force microscopy (AFM) in chemical force mapping (CFM) mode to measure adhesion using tips functionalized with alkyl, -CH3. By combining adhesion forces measured as a function of pH, with data from streaming potential experiments and DLVO calculations, we were able to determine the surface charge density. We observed increased adhesion between the mineral surface and the hydrophobic tips as the contact time increased from 7 ms to ∼2 s. The diffusion of dissolved ions takes time, and density functional theory (DFT) calculations did not indicate a strong hydration of the mineral surfaces. Therefore, we interpret that the loss of ions from the confined space between the tip and sample is a likely explanation of the correlation between the dwell time and adhesion. The maximum adhesion increase with dwell time for muscovite, i.e., 400 ± 77 pN, was considerably larger than for quartz, 84 ± 15 pN, which fits with the different surface structure and composition of the two minerals. We propose two mechanisms to explain these results: (1) cations that are structured in the solution and on the surface remain associated at the tip-sample interface initially but diffuse away during extended contact time and (2) adventitious carbon, the organic material that comes spontaneously from air and solution, can diffuse to the tip-sample interface during contact. This material decreases the surface energy by aggregating near the alkyl tip and increases adhesion between the tip and sample.

Change in organic molecule adhesion on α-alumina (sapphire) with change in NaCl and CaCl2 solution salinity.

We investigated the adhesion of two functional groups to α-alumina as a model for the adsorption of organic molecules on clay minerals. Interactions between organic compounds and clay minerals play an important role in processes such as drinking water treatment, remediation of contaminated soil, oil recovery, and fabricating complicated nanomaterials, and there have been claims that organic compound-clay mineral interaction created the ordering that is necessary for the genesis of life. In many organisms, interaction between organic molecules and biominerals makes it possible to control the growth of bones, teeth, and shells. Adhesion of carboxylic acid, -COO(H), and pyridine, -C5H5N(H(+)), on the {0001} plane of α-alumina wafers has been investigated with atomic force microscopy (AFM) in chemical force mapping (CFM) mode. Both functional groups adhered to α-alumina in deionized water at pH < 5, and adhesion decreased as NaCl or CaCl2 concentration increased. X-ray photoelectron spectroscopy (XPS) showed that Na(+) and Ca(2+) adsorbed to the α-alumina surface at pH < 5, decreasing surface interaction with the carboxylic acid and pyridine groups. We interpret the results as evidence that the tips adhere to alumina through hydrogen bonding when only water is present. In solutions containing NaCl and CaCl2, cations are adsorbed but Cl(-) is not. When NaCl solutions are replaced by CaCl2, Ca(2+) replaces Na(+), but rinsing with ultrapure deionized water (pH 5.6) could not restore the original protonated surface. The results demonstrate that the alumina surface at pH 3 has a higher affinity for inorganic cations than for -COO(H) or -C5H5N(H(+)), in spite of the known positive surface charge of α-alumina {0001} wafers. These results demonstrate that solution salinity plays an important role in surface properties, controlling surface tension (i.e., contact angle) and adsorption affinity on α-alumina and, by analogy, on clay minerals.

Infrared spectroscopy and density functional theory investigation of calcite, chalk, and coccoliths--do we observe the mineral surface?

We have measured infrared spectra from several types of calcite: chalk, freshly cultured coccoliths produced by three species of algae, natural calcite (Iceland Spar), and two types of synthetic calcite. The most intense infrared band, the asymmetric carbonate stretch vibration, is clearly asymmetric for the coccoliths and the synthetic calcite prepared using the carbonation method. It can be very well fitted by two peaks: a narrow Lorenzian at lower frequency and a broader Gaussian at higher frequency. These two samples both have a high specific surface area. Density functional theory for bulk calcite and several calcite surface systems allows for assignment of the infrared bands. The two peaks that make up the asymmetric carbonate stretch band come from the bulk (narrow Lorenzian) and from a combination of two effects (broad Gaussian): the surface or near surface of calcite and line broadening from macroscopic dielectric effects. We detect water adsorbed on the high surface area synthetic calcite, which permits observation of the chemistry of thin liquid films on calcite using transmission infrared spectroscopy. The combination of infrared spectroscopy and density functional theory also allowed us to quantify the amount of polysaccharides associated with the coccoliths. The amount of polysaccharides left in chalk, demonstrated to be present in other work, is below the IR detection limit, which is 0.5% by mass.

Controlling biomineralisation with cations.

The production of polymers for controlling calcite growth is a well-known approach in biomineralising organisms. Numerous studies have shown that polymers significantly influenced the growth rate and morphology of CaCO3 but little is known about how the polymers are actually controlled by the organisms. Here we show that cations control the effect of polysaccharides and that these processes have been in place for at least 60 million years. We studied the interaction between cleaved samples of pure calcite and ancient coccolith associated polysaccharides (aPS) that we had extracted from the samples of Cretaceous chalk, in solutions that contained one of the common seawater cations, K+, Ca2+, Mg2+ and Sr2+. With atomic and chemical force microscopy (AFM and CFM), we showed that K+, Ca2+ and Sr2+ complex aPS through a weak, outer sphere bonding, giving the aPS affinity to sites on steps and terraces. In contrast, Mg2+ enhanced the formation of stronger and longer aPS complexes, resulting in low affinity to calcite terraces and strong affinity to steps. It is known that adsorption is influenced by ionic potential and ionic strength. Our results show that cation-polysaccharide complexing can modify the effectiveness of the polymer. Thus, creating organic molecules with cation complexing ability is an effective strategy for regulating mineral growth, both now and in the past.

Investigating the long-term effect of subchronic phencyclidine-treatment on novel object recognition and the association between the gut microbiota and behavior in the animal model of schizophrenia.

Subchronic phencyclidine (subPCP) treatment induces schizophrenic-like behavior in rodents, including cognitive deficits and increased locomotor sensitivity towards acute administration of PCP. Evidence is accumulating that the gut microbiota (GM) influences behavior through modulation of the microbiota-gut-brain axis, and hence, part of the variation within this animal model may derive from variation in the GM. The aims of this study was to investigate first, the duration of subPCP-induced cognitive impairment in the novel object recognition test, and second, the possible effect of subchronic PCP-treatment on the GM, and the association between the GM and the behavioral parameters. The association was further investigated by antibiotic reduction of the GM. Male Lister Hooded rats were dosed twice daily i.p. with either 5mg/kg PCP or sterile isotonic saline for seven days followed by a seven-day washout period. Rats were tested in the novel object recognition and the locomotor activity assays immediately after, three weeks after, or six weeks after washout, and the fecal GM was analyzed by high throughput sequencing. Antibiotic- and control-treated rats were tested in the same manner following washout. In conclusion, subPCP-treatment impaired novel object recognition up to three weeks after washout, whereas locomotor sensitivity was increased for at least six weeks after washout. Differences in the core gut microbiome immediately after washout suggested subPCP treatment to alter the GM. GM profiles correlated to memory performance. Administration of ampicillin abolished the subPCP-induced memory deficit. It thus seems reasonable to speculate that the GM influences memory performance, contributing to variation within the model.

Hearing at low and infrasonic frequencies.

The human perception of sound at frequencies below 200 Hz is reviewed. Knowledge about our perception of this frequency range is important, since much of the sound we are exposed to in our everyday environment contains significant energy in this range. Sound at 20-200 Hz is called low-frequency sound, while for sound below 20 Hz the term infrasound is used. The hearing becomes gradually less sensitive for decreasing frequency, but despite the general understanding that infrasound is inaudible, humans can perceive infrasound, if the level is sufficiently high. The ear is the primary organ for sensing infrasound, but at levels somewhat above the hearing threshold it is possible to feel vibrations in various parts of the body. The threshold of hearing is standardized for frequencies down to 20 Hz, but there is a reasonably good agreement between investigations below this frequency. It is not only the sensitivity but also the perceived character of a sound that changes with decreasing frequency. Pure tones become gradually less continuous, the tonal sensation ceases around 20 Hz, and below 10 Hz it is possible to perceive the single cycles of the sound. A sensation of pressure at the eardrums also occurs. The dynamic range of the auditory system decreases with decreasing frequency. This compression can be seen in the equal-loudness-level contours, and it implies that a slight increase in level can change the perceived loudness from barely audible to loud. Combined with the natural spread in thresholds, it may have the effect that a sound, which is inaudible to some people, may be loud to others. Some investigations give evidence of persons with an extraordinary sensitivity in the low and infrasonic frequency range, but further research is needed in order to confirm and explain this phenomenon.

Adjusting mobility scales of ion mobility spectrometers using 2,6-DtBP as a reference compound.

Performance of several time-of-flight (TOF) type ion mobility spectrometers (IMS) was compared in a joint measurement campaign and their mobility scales were adjusted based on the measurements. A standard reference compound 2,6-di-tert butylpyridine (2,6-DtBP) was used to create a single peak ion mobility distribution with a known mobility value. The effective length of the drift tube of each device, considered here as an instrument constant, was determined based on the measurements. Sequentially, two multi-peaked test compounds, DMMP and DIMP, were used to verify the performance of the adjustment procedure in a wider mobility scale. By determining the effective drift tube lengths using 2,6-DtBP, agreement between the devices was achieved. The determination of effective drift tube lengths according to standard reference compound was found to be a good method for instrument inter-comparison. The comparison procedure, its benefits and shortcomings as well as dependency on accuracy of literature value are discussed along with the results.

A 41-year history of a mandibular subperiosteal implant.

The subperiosteal implant was originally described in the 1940s. The inadequate long-term results of subperiosteal implants are in contrast to the excellent results documented for endosseous osseointegrated oral implants. Consequently, subperiosteal implants and other soft-tissue-anchored implants should not be used presently. Furthermore, these implants are seldom seen today, because they generally were removed rather shortly after placement. The present report documents a full 41-year history of a mandibular subperiosteal implant inserted in 1957 by focusing upon the consequences of not removing an implant in spite of continuous periods of complications during 4 decades. Implant exposure, inflammation, infection, and fistula formation occurred persistently. Total implant removal was refused by the patient in 1973. After 25 years without control, tremendous resorption of the mandible was observed in 1998. Consequently, the entire implant was then removed. Placement of osseointegrated oral implants was impossible without extensive autogenous bone grafting. The present report has demonstrated that regular control of patients with subperiosteal implants is mandatory. Furthermore, subperiosteal implants should definitely be removed, if continuous periods of complications occur.

Marginal tissue response adjacent to Astra Dental Implants supporting overdentures in the mandible.

The aim of this study was to evaluate the marginal tissue response adjacent to implant supported overdentures. Twenty edentulous patients had 2 Astra Dental Implants placed in the canine region of the lower jaw. New overdentures were retained by individual ball attachments in 11 patients and by a bar attachment in 9 patients. Periodontal registrations were recorded 0 months, 6 months, 12 months and 24 months after the overdentures were inserted. One of the 40 fixtures was lost at the stage of abutment connection. No fixtures were lost during the 2- to 4-year observation period and no fixtures showed any periodontal signs of failure. At the 2-year examination, no pocket depths adjacent to the implants exceeded 4 mm and no bone loss exceeded 3 mm. The mean annual bone loss was less than 0.2 mm during the first 2 years. The preliminary results from this limited study were promising and showed that two osseointegrated Astra Dental Implants could successfully retain an overdenture in the lower jaw. However, long-term observation is needed for a definitive evaluation of this treatment concept.