Effect of adsorption of organic solvents on the band profiles in reversed-phase non-linear chromatography

The influence of the mobile phase composition on the adsorption equilibria in non-linear reversed-phase chromatography has been investigated. RP-18 and RP-18 endcapped columns have been selected with methanol-water and acetonitrile-water as a mobile phase and cyclopentanone as a solute. Due to its structure, cyclopentanone exhibited affinity to the active adsorption sites on alkyl chains as well as to the polar, uncovered surface of the adsorbent. The adsorption equilibria of solvents—methanol-water, acetonitrile-water on RP-18 and RP-18e columns—have been measured and the excess adsorption isotherms accounting for non-ideality of the mobile and adsorbed phase have been determined. The competitive heterogeneous adsorption model for the solute and organic solvent has been proposed and coupled with a model of column dynamics. The model predictions have been verified by comparison to experimental chromatograms.     

Reconfiguration of Amorphous Complex Oxides: A Route to a Broad Range of Assembly Phenomena,Hybrid Materials,and Novel Functionalities

Reconfiguration of amorphous complex oxides provides a readily controllable source of stress that can be leveraged in nanoscale assembly to access a broad range of 3D geometries and hybrid materials. An amorphous SrTiO₃ layer on a Si:B/Si_1?xGe_x:B heterostructure is reconfigured at the atomic scale upon heating, exhibiting a change in volume of ≈2% and accompanying biaxial stress. The Si:B/Si_1?xGe_x:B bilayer is fabricated by molecular beam epitaxy, followed by sputter deposition of SrTiO₃ at room temperature. The processes yield a hybrid oxide/semiconductor nanomembrane. Upon release from the substrate, the nanomembrane rolls up and has a curvature determined by the stress in the epitaxially grown Si:B/Si_1?xGe_x:B heterostructure. Heating to 600 °C leads to a decrease of the radius of curvature consistent with the development of a large compressive biaxial stress during the reconfiguration of SrTiO₃. The control of stresses via post-deposition processing provides a new route to the assembly of complex-oxide-based heterostructures in 3D geometry. The reconfiguration of metastable mechanical stressors enables i) synthesis of various types of strained superlattice structures that cannot be fabricated by direct growth and ii) technologies based on strain engineering of complex oxides via highly scalable lithographic processes and on large-area semiconductor substrates.     

Exopolysaccharide Carbohydrate Structure and Biofilm Formation by Rhizobium leguminosarum bv. trifolii Strains Inhabiting Nodules of Trifolium repens Growing on an Old Zn–Pb–Cd-Polluted Waste Heap Area

Heavy metals polluting the 100-year-old waste heap in Bolesław (Poland) are acting as a natural selection factor and may contribute to adaptations of organisms living in this area, including Trifolium repens and its root nodule microsymbionts—rhizobia. Exopolysaccharides (EPS), exuded extracellularly and associated with bacterial cell walls, possess variable structures depending on environmental conditions; they can bind metals and are involved in biofilm formation. In order to examine the effects of long-term exposure to metal pollution on EPS structure and biofilm formation of rhizobia, Rhizobium leguminosarum bv. trifolii strains originating from the waste heap area and a non-polluted reference site were investigated for the characteristics of the sugar fraction of their EPS using gas chromatography mass-spectrometry and also for biofilm formation and structural characteristics using confocal laser scanning microscopy under control conditions as well as when exposed to toxic concentrations of zinc, lead, and cadmium. Significant differences in EPS structure, biofilm thickness, and ratio of living/dead bacteria in the biofilm were found between strains originating from the waste heap and from the reference site, both without exposure to metals and under metal exposure. Received results indicate that studied rhizobia can be assumed as potentially useful in remediation processes.     

Gas chromatographic analysis with chiral cyclodextrin phases reveals the enantioselective formation of hydroxylated polychlorinated biphenyls by rat liver microsomes

Chiral PCB congeners are major components of PCB mixtures and undergo enantioselective biotransformation to hydroxylated (OH-)PCBs by cytochrome P450 enzymes. While it is known that biotransformation results in an enantiomeric enrichment of the parent PCB, it is currently unknown if OH-PCBs are formed enantioselectively. The present study screened seven commercial capillary gas chromatography columns containing modified β- or γ-cyclodextrins for their potential to separate the atropisomers of methylated derivatives of OH-PCB. The atropisomers of 3-, 4- and 5-methoxy derivatives were at least partially separated on one or more columns. A subsequent biotransformation study was performed with rat liver microsomes to assess if hydroxylated metabolites are formed enantioselectively from PCBs 91, 95, 132, and 149. The OH-PCBs were extracted from the microsomal incubations, derivatized with diazomethane and analyzed as the respective methoxylated (MeO-)PCB derivatives using selected columns. The 5-hydroxylated metabolites of PCBs 91, 95, 132, and 149 were the major metabolites, which is consistent with PCB's biotransformation by cytochrome P450 2B enzymes. All 5-hydroxylated metabolites displayed a clear, congener-specific enantiomeric enrichment. Overall, this study demonstrates for the first time that chiral PCBs, such as PCB 91, 95, 132, and 149, are enantioselectively metabolized to OH-PCBs by cytochrome P450 enzymes.     

Electronic speckle pattern shearing interferometer with a photopolymer holographic grating

A photopolymer holographic grating is used to produce the two sheared images in an electronic speckle pattern shearing interferometer. A ground glass screen following the grating eliminates unwanted diffraction orders and removes the requirement for the CCD camera to resolve the diffraction grating's pitch. The sheared images on the ground glass are further imaged onto the CCD camera. The fringe pattern contrast was estimated to be above 90%. A validation of the system was done by comparing the theoretical phase difference distribution with the experimental data from the three-point bending test.     

Investigation of the diffusion processes in a self-processing acrylamide-based photopolymer system

Results from the investigation of the diffusion processes in a dry acrylamide-based photopolymer system are presented. The investigation is carried out in the context of experimental research on optimization of the high-spatial-frequency response of the photopolymer. Tracing the transmission holographic grating dynamics at short times of exposure is utilized to measure diffusion coefficients. The results reveal that two different diffusion processes contribute with opposite sign to the refractive-index modulation responsible for the diffraction grating buildup. Monomer diffusion from dark to bright fringe areas increases the refractive-index modulation. It is characterized with diffusion constant D0 = 1.6 x 10(-7) cm2/s. A second diffusion process takes place during the recording. It decreases the refractive-index modulation and we ascribe it to diffusion of short-chain polymer molecules or radicals from bright to dark fringe areas. The estimated diffusion coefficient for this process is D0 = 6.35 x 10(-10) cm2/s. The presence of the second process could be responsible for the poor high-spatial-frequency response of the investigated photopolymer system. Comparison with the diffusion in photopolymer systems known for their good response at high spatial frequencies shows that both investigated diffusion processes occur in a much faster time scale.     

Multidisciplinary approach to the assessment of historic structures based on the case of a masonry bridge in Galicia (Spain)

The paper presents a general method to evaluate a masonry structure with a complex geometry and unknown material properties. This multidisciplinary approach integrates close range digital photogrammetry, ground probing radar (GPR) and finite elements analysis (FEM) to analyse a masonry bridge. The resulting information from photogrammetry and radar is applied to define a 3D model, which is then used to simulate the behaviour of the bridge using FEM. Two different approaches to model the internal composition of the bridge with finite elements are presented. Sensitivity analysis is applied to study the reasons of the structural damage.     

Colour Change in Heated Concrete

This paper presents an analysis of colour change in concrete under the influence of heat. The colour change observed in concrete is primarily a result of the gradual dehydration of the cement paste, but also of transformations occurring within the aggregate. The colour change may be used to reveal the exposure temperature of concrete from which the corresponding fire damage of concrete can be estimated. The paper presents the results of tests carried out on ordinary and high performance concretes (OC and HPC) prepared with natural river-bed aggregates. In addition, mortars and cement pastes prepared with the same components were observed to change colour upon heating. The colour change was investigated using Scion Image v. 4.0.3, an image analysis software package (Scion Corporation ©, USA). In the proposed method the digital image is split into three RGB colour components: red, green and blue, which are then presented as a histogram using counts of pixel intensity. The histogram results show colour distributions in unheated cementitious material and in material heated to temperatures ranging from 100°C to 1000°C. The concrete colour changes as a result of heating are linked to the physical and chemical transformations taking place in the heated material.