Adsorption of trimethyl phosphate on maghemite, hematite, and goethite nanoparticles

Adsorption of trimethyl phosphate (TMP) on well-characterized hematite, maghemite and goethite nanoparticles was studied by in situ DRIFT spectroscopy as a model system for adsorption of organophosphorous (OP) compounds on iron minerals. The iron minerals were characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), specific surface area, and pore size distribution. The minerals were found to consist of stoichimetrically and morphologically well-defined maghemite, hematite, and goethite nanoparticles. Analysis of in situ diffuse reflectance Fourier transform (DRIFT) spectroscopy shows that TMP bonds mainly to Lewis acid Fe sites through the O phosphoryl atom (-P═O-Fe) on hematite and maghemite. On goethite most TMP molecules bond to Br?nstedt acid surface OH groups and form hydrogen bonded surface complexes. The vibrational mode analysis and uptake kinetics suggest two main reasons for the observed trend of reactivity toward TMP (hematite > maghemite > goethite): (i) larger number of accessible Lewis acid adsorption sites on hematite; (ii) stronger interaction between the Lewis acid Fe sites and the phosphoryl O atom on TMP for hematite and maghemite compared to goethite with concomitant formation of surface coordinated TMP and dimethyl phosphate intermediates. As a result, on the oxides a surface oxidation pathway dominates during the initial adsorption, which results in the formation of surface methoxy and formate. In contrast, on goethite a slower hydrolysis pathway is identified, which eventually yields phosphoric acid. The observed trends of the reactivity and analysis of the corresponding surface structure and particle morphology suggest an intimate relation between the surface chemistry of exposed crystal facets on the iron minerals. These results are important to understand OP surface chemistry on iron minerals.     

Comparative characterization of oligomeric precursors intended for injectable implants

The use of injectable materials is a simple approach for drug delivery and tissue repair, in, e.g. minimally invasive surgery applications. If these materials are used past their glass transition temperature and have a low viscosity, they will be able to flow while delivered in situ. Whether these materials are to be used as low viscosity drug carriers or further crosslinked for tissue repair, there is a need for a better understanding of their handling properties. In this study, oligo(trimethylene carbonate) (oTMC) and oligo[D,L‐lactide‐co‐(ε‐caprolactone)] (oDLLA‐co‐CL) of various molecular weights within a relevant injectability range were synthesized via ring‐opening polymerization. The materials were comparatively characterized by ¹H NMR spectroscopy, differential scanning calorimetry, gel permeation chromatography, and rheological measurements. After comparing the viscosities and molecular weights of the materials, it was concluded that oDLLA‐co‐CLs were, generally, better suited as an injectable in situ crosslinking network, whereas oTMCs were found to be better candidates as injectable drug carriers. This study provides useful data and guidelines on the use of these and other similar oligomers intended for injectable implants. Copyright © 2012 John Wiley & Sons, Ltd.     

Adsorption mechanisms of glucose in aqueous goethite suspensions

The adsorption of glucose and polysaccharides onto solid surfaces is important in several areas of science and engineering including soil chemistry and mineral processing. In this work we have studied the adsorption of D-glucose at the water-goethite (α-FeOOH) interface as a function of pH using batch adsorption measurements and a simultaneous infrared and potentiometric technique. Molecular orbital calculations were also performed in order to support interpretations of the infrared spectroscopic data. Infrared spectroscopy has shown that glucose adsorbs at the water-goethite interface with an intact ring structure and that the β-form is favored relative to the α isomer. The collective spectroscopic and macroscopic results were fully consistent with an adsorption mechanism where glucose interacts with goethite surface sites via hydrogen bonding interactions. Specific infrared peak shifts indicated that glucose primarily acts as a hydrogen bond donor and that it interacts with acceptor sites that become increasingly more prevalent as the surface is deprotonated. These results are in general agreement with the acid/base model for mono- and polysaccharide interactions at metal oxide surfaces, but contradict the inner sphere hypothesis that was proposed based on ex situ spectroscopic measurements.     

Zero Modes for the Magnetic Pauli Operator in Even-Dimensional Euclidean Space

We study the ground state of the Pauli Hamiltonian with a magnetic field in ${\mathbb{R}^{2d}}$ , d > 1. We consider the case where a scalar potential W is present and the magnetic field B is given by ${B=2i\partial\bar{\partial} W}$ . The main result is that there are no zero modes if the magnetic field decays faster than quadratically at infinity. If the magnetic field decays quadratically then zero modes may appear, and we give a lower bound for the number of them. The results in this paper partly correct a mistake in a paper from 1993.     

Evolution of energy spectrum from laser-accelerated protons with a 100 fs intense prepulse

A parametric study is reported where a femtosecond prepulse is used to change the target properties before the interaction with a multi-terawatt laser pulse which accelerates protons from a foil target. The proton spectrum as function of the prepulse delay and intensity, up to 1.5 ns and up to 3×10¹⁶ W/cm², respectively, shows a global decrease of the maximum proton energy with delay and intensity. However, under appropriate conditions, it is found that the maximum proton energy increases by more than 10% and that the spectral shape changes.     

Molecular dynamics study of contact mechanics: contact area and interfacial separation from small to full contact

We report a molecular dynamics study of the contact between a rigid solid with a randomly rough surface and an elastic block with a flat surface. We study the contact area and the interfacial separation from small contact (low load) to full contact (high load). For small load the contact area varies linearly with the load and the interfacial separation depends logarithmically on the load. For high load the contact area approaches the nominal contact area (i.e., complete contact), and the interfacial separation approaches zero. The present results may be very important for soft solids, e.g., rubber, or for very smooth surfaces, where complete contact can be reached at moderate high loads without plastic deformation of the solids.     

Frictional properties of confined polymers

We present molecular dynamics friction calculations for confined hydrocarbon solids with molecular lengths from 20 to 1400 carbon atoms. Two cases are considered: a) polymer sliding against a hard substrate, and b) polymer sliding on polymer. In the first setup the shear stresses are relatively independent of molecular length. For polymer sliding on polymer the friction is significantly larger, and dependent on the molecular chain length. In both cases, the shear stresses are proportional to the squeezing pressure and finite at zero load, indicating an adhesional contribution to the friction force. The friction decreases when the sliding distance is of the order of the molecular length indicating a strong influence of molecular alignment during run-in. The results of our calculations show good correlation with experimental work.     

K‐edge XANES analysis of sulfur compounds: an investigation of the relative intensities using internal calibration

Sulfur K‐edge XANES (X‐ray absorption near‐edge structure) spectroscopy is an excellent tool for determining the speciation of sulfur compounds in complex matrices. This paper presents a method to quantitatively determine the kinds of sulfur species in natural samples using internally calibrated reference spectra of model compounds. Owing to significant self‐absorption of formed fluorescence radiation in the sample itself the fluorescence signal displays a non‐linear correlation with the sulfur content over a wide concentration range. Self‐absorption is also a problem at low total absorption of the sample when the sulfur compounds are present as particles. The post‐edge intensity patterns of the sulfur K‐edge XANES spectra vary with the type of sulfur compound, with reducing sulfur compounds often having a higher post‐edge intensity than the oxidized forms. In dilute solutions (less than 0.3–0.5%) it is possible to use sulfur K‐edge XANES reference data for quantitative analysis of the contribution from different species. The results show that it is essential to use an internal calibration system when performing quantitative XANES analysis. Preparation of unknown samples must take both the total absorption and possible presence of self‐absorbing particles into consideration.     

Sorption of Bisphenol A as Model for Sorption Ability of Organoclays

The arrangement of bisphenol A molecules into organoclays and their interactions with the intercalated surfactant were studied. The organoclays were prepared via solid-state intercalation of four cationic surfactants, such as dodecyltrimethyl-, tetradecyltrimethyl-, hexadecyltrimethyl-, and didodecyldimethyl-ammonium, as bromide salts, at different loading levels into the interlayers of two natural clays. The natural clays, the prepared organoclays, and the spent organoclays were characterized by X-ray powder diffraction, infrared spectroscopy, and scanning electron microscopy. X-ray powder diffraction measurements showed successive interlayer expansions of the d₀₀₁ basal spacing due to the intercalation of the cationic surfactants and the bisphenol A sorption. The increased d₀₀₁ basal spacing of the organoclays after bisphenol A sorption indicates that the molecules are integrated between the alkyl chains of the surfactant in the organoclays interlayers. Infrared spectroscopy was employed to probe the intercalation of the cationic surfactants and the sorbed bisphenol A. New characteristic bands attributed to the bisphenol A phenol rings appear in the range 1518–1613 cm⁻¹ on the infrared spectra of the spent organoclays, proving the presence of bisphenol A in the hydrophobic interlayers. Scanning electron microscopy of the organoclays before and after BPA sorption shows that their morphology becomes fluffy and that the presence of the organic molecules expands the clay structure.