Fibronectin adsorption on tantalum: the influence of nanoroughness

The complex mechanisms of protein adsorption at the solid-liquid interface is of great importance in many research areas, including protein purification, biocompatibility of medical implants, biosensing, and biofouling. The protein adsorption process depends crucially on both the nanoscale chemistry and topography of the interface. Here, we investigate the adsorption of the cell-binding protein fibronectin on flat and nanometer scale rough tantalum oxide surfaces using ellipsometry and quartz crystal microbalance with dissipation (QCM-D). On the flat tantalum oxide surfaces, the interfacial protein spreading causes an increase in the rigidity and a decrease in the thickness of the adsorbed fibronectin layer with decreasing bulk protein concentration. For the tantalum oxide surfaces with well-controlled, stochastic nanometer scale roughness, similar concentration effects are observed for the rigidity of the fibronectin layer and saturated fibronectin uptake. However, we find that the nanorough tantalum oxide surfaces promote additional protein conformational changes, an effect especially apparent from the QCM-D signals, interpreted as an additional stiffening of the formed fibronectin layers.     

A new method for assigning common spot boundaries for multiple gels in two-dimensional gel electrophoresis

The benefits of defining common spot boundaries when several gels from 2-DE are compared and analyzed have lately been stressed by both commercial software producers and users of this software. Though the importance of common spot boundaries is clearly stated, few reports exist that target this issue explicitly. In this study a method for defining common spots boundaries is developed, called the spot density method. The method consists of the following steps: segmentation and spot identification on each individual gel, transferring the spot-center coordinates for all gels onto a single new gel, collecting spot centers clustered together in the new gel and finally assigning pixels and new spot boundaries based on the spots in each cluster. The method is compared to a synthetic gel approach, and validated by visual inspection of three representative areas in the gels. The gel images need to be aligned prior to segmentation and spot identification, but the method can be used regardless of the choice of segmentation procedure. This makes the method an easy extension to existing methods for spot identification and matching. Conclusions based on the visual inspection are that the spot density method identifies partly overlapping spots and low-intensity spots better than the synthetic gel approach.     

Fibronectin adsorption on gold, Ti-, and Ta-oxide investigated by QCM-D and RSA modelling

The adsorption of fibronectin on gold, Ti-, and Ta-oxide surfaces is investigated by means of the quartz crystal microbalance with dissipation (QCM-D) technique. The surface chemistry (gold, Ti-, and Ta-oxide) is found to influence the frequency shift observed during adsorption of the fibronectin layer with the magnitude being Delta f Au>Delta f Ti-oxide approximately Delta f Ta-oxide. Corresponding variations in the dissipation change normalised to frequency change (Delta D/Delta f) for the layer are observed. The QCM-D data are further analyzed by the random sequential adsorption (RSA) model, and adsorption rate parameter ka and footprint (a) determined, which supported the trend seen in the Delta f and Delta D/Delta f values. The value of ka found by the RSA modelling of the QCM-D resonance frequency data is found to match the ratio between the mass measured by QCM-D and the mass reported by optical techniques in literature. We conclude that comparison of the adsorption rate parameter (ka) obtained by RSA modelling of the QCM-D data with ka values obtained from RSA modelling of data obtained using optical techniques can be a route to determine the degree of hydration of the adsorbed protein layer.     

UV light-assisted mineralisation and biodetoxification of Ponceau S with hydroxyl and sulfate radicals

The present study reports simultaneous mineralisation and biodetoxification of Ponceau S (3-hydroxy-4-(2-sulfo-4-[4-sulfophenylazo]phenylazo)-2,7-naphthalenedisulfonic acid sodium salt), an azo dye, by UV light assisted oxidation with hydroxyl and sulfate radicals. Metal ion catalysts used in the work were: Fe²⁺ and Ag⁺, and the oxidants used were: hydrogen peroxide and S₂O₈^2?. Strategies adopted to make the processes environmentally benign and economically viable by achieving maximum mineralisation in the shortest possible time are described. Mineralisation efficiency (Em) of various systems was found to follow the order: E_m(Fe²⁺/H₂O₂/UV) > E_m(Fe²⁺/S₂O₈^2?/UV) > E_m(Ag⁺/H₂O₂/UV) ≈ E_m(Ag⁺/S₂O₈^2?/UV). Thus, Fe²⁺ and HP are the most suitable metal ion catalyst and oxidant respectively, showing higher efficiency at pH 3 followed by that at pH 6.6. It is possible to enhance the Fe²⁺/H₂O₂/UV process electrical energy efficiency by maintaining the concentration of Fe at either 0.05 mM or 0.03 mM and that of the oxidant at 2.5 mM. The bioassay study revealed that the Fe²⁺/S₂O₈^2?/UV process biodetoxification efficiency is higher at pH 3 (93.7 %) followed by that at pH 6.6 (80.1 %) at the concentration of Fe ²⁺ and S₂O₈^2? of 0.03 mM and 2.5 mM, respectively. Thus, not only the concentration of Fe²⁺, but also the nature of the oxidant and pH play an important role in the biodetoxification process and S₂O₈^2? possesses higher biodetoxification efficiency than H₂O₂.     

The inconsistency in adsorption properties and powder XRD data of MOF-5 is rationalized by framework interpenetration and the presence of organic and inorganic species in the nanocavities

MOF-5 is the archetype metal-organic framework and has been subjected to numerous studies the past few years. The focal point of this report is the pitfalls related to the MOF-5 phase identification based on powder XRD data. A broad set of conditions and procedures have been reported for MOF-5 synthesis. These variations have led to materials with substantially different adsorption properties (specific surface areas in the range 700 to 3400 m(2)/g). The relatively low weight loss observed for some as synthesized samples upon solvent removal is also indicative of a low pore volume. Regrettably, these materials have all been described as MOF-5 without any further comments. Furthermore, the reported powder XRD patterns hint at structural differences: The variations in surface area are accompanied by peak splitting phenomena and rather pronounced changes in the relative peak intensities in the powder XRD patterns. In this work, we use single-crystal XRD to investigate structural differences between low and high surface area MOF-5. The low surface area MOF-5 sample had two different classes of crystals. For the dominant phase, Zn(OH)2 species partly occupied the cavities. The presence of Zn species makes the hosting cavity and possibly also adjacent cavities inaccessible and thus efficiently reduces the pore volume of the material. Furthermore, the minor phase consisted of doubly interpenetrated MOF-5 networks, which lowers the adsorption capacity. The presence of Zn species and lattice interpenetration changes the symmetry from cubic to trigonal and explains the peak splitting observed in the powder XRD patterns. Pore-filling effects from the Zn species (and partly the solvent molecules) are also responsible for the pronounced variations in powder XRD peak intensities. This latter conclusion is particularly useful for predicting the adsorption properties of a MOF-5-type material from powder XRD.     

Synthesis of functionalized, unsymmetrical 1,3,4,6-tetrasubstituted 2,5-diketopiperazines

A general and efficient method for the synthesis of unsymmetrical 1,3,4,6-tetrasubstituted 2,5-diketo- piperazines (DKPs) is described. Cyclization of N-amide alkylated dipeptide methyl esters, followed by alkylation, furnished the corresponding tetrasubstituted DKPs in good overall yields. The influence of steric hindrance in the alkylation reactions appeared to be of lesser importance as long as reactive alkylating agents were used. Furthermore, we have demonstrated the use of tetrasubstituted DKPs as a scaffold for further chemical manipulations to produce novel DKPs with desired properties.     

Kinetics of dichlorosilylene trapping by methane and mechanism and kinetics of the methyldichlorosilane decomposition

Data relative to methane trapping of SiCl₂ and a rate constant for the SiCl₂ into C(SINGLEBOND)H bond insertion process of k₋₁=13.4 M⁻¹s⁻¹ at 921 K are reported. Results on the decomposition of the trapping product, methyldichlorosilane, are also reported. This decomposition follows first-order kinetics with a rate constant of k=1.5±0.2×10⁻³ s⁻¹ at 905 K and produces methane, trichlorosilane, methyltrichlorosilane, and tetrachlorosilane. It is argued that the decomposition involves silylene intermediates, is nonchain, and is initiated primarily by the molecular methane elimination process MeSiHCl₂(SINGLEBOND)1→ CH⁴+SiCl₂. Free radicals and Si(SINGLEBOND)C bond fission may also contribute to the decomposition but are not dominant. The kinetics of MeSiHCl₂ decomposition are shown to be consistent with the kinetics of the reverse SiCl₂/CH₄ trapping reaction and with the overall reaction thermochemistry. Reaction modeling gives product yields, reactant conversions, and rates in reasonable agreement with the data. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 89–97, 1998.     

Vortex imaging in Co-doped BaFe2As2

We review superconducting vortex imaging in Co-doped BaFe₂As₂ by Bitter decoration and small-angle neutron scattering (SANS). At all measured fields a highly disordered vortex configuration is observed, which is attributed to strong pinning. Further support of this conclusion comes from the absence of a Meissner rim in decoration images obtained close to the sample edge. The evolution of the SANS scattering vector with increasing applied field indicates vortex lattice domains of (distorted) hexagonal symmetry. This is consistent with the decoration images which show small, six fold coordinated ordered vortex domains. The SANS scattered intensity is found to decrease rapidly with increasing field, exceeding the rate expected from estimates of the upper critical field. This is consistent with the large degree of vortex “lattice” disorder.