Understanding adsorption phenomena: investigation of the dye-cellulose interaction

To understand the structural factors that control the adsorption of acid dyes onto cotton (cellulose), the adsorption of 15 acid dyes from water has been studied. An equilibrium exists between dye adsorbed in the cotton and dye in solution, and by measurement of the temperature dependence (277-333K) of the equilibrium constant, the enthalpy and entropy of binding are obtained. For most dyes adsorption is driven by the binding enthalpy, which is ascribed to van der Waals forces. Acid dyes consist of an aromatic core with peripheral solubilizing groups (generally sulfonates). Dyes in which the sulfonates are on one side of the molecule have the largest binding enthalpy. Assuming a binding geometry where the sulfonates protrude into water pools in the bulk amorphous regions and as much as possible of the dye core touches the surface, then a good correlation exists between the binding enthalpy and the summation of 1/r(6) over all the C, N, and O dye atoms, where r is the distance of each atom from the cellulose surface.     

High-field NMR using resistive and hybrid magnets

Resistive and resistive-superconducting hybrid magnets can generate dc magnetic fields much higher than conventional superconducting NMR magnets but the field spatial homogeneity and temporal stability are usually not sufficient for high-resolution NMR experiments. Hardware and technique development addressing these issues are presented for high-resolution NMR at magnetic fields up to 40T. Passive ferromagnetic shimming and magic-angle spinning are used effectively to reduce the broadening from inhomogeneous magnetic field. A phase correction technique based on simultaneous heteronuclear detection is developed to compensate magnetic field fluctuations to achieve high spectral resolution.     

A simple method for extracting both active oily and water soluble extract (WSE) from Nigella sativa (L.) seeds using a single solvent system

The current study provides a way of extraction for both active NSO and WSE from Nigella sativa seeds using 98% methanol. About 1?kg of ground seeds was macerated by 1:2.5 w/v (g/mL) for 72?hours. After rotary evaporation and 7 days of continuous drying and chilling at 50 and 4?°C, NSO and WSE were obtained at the same instant. Solubility tests of 24 solvents and 11 thin layer chromatographic analyses while 2, 2-diphenyl-1-picrylhydrazyl free radical scavenging assay of NSO (73.66) , WSE (33.32) and NSO?+?WSE (78.22) against ascorbic acid (IC50?=?4.28?mg/mL) was performed. WSE was found to be highly soluble in water and 5% NaOH exhibiting the same Rf value of 0.95 for EtOH:DMSO (9:1) against the honey. WSE has revealed more than twofold higher anti-oxidant activity than others. Formulation of WSE with Tualang honey may provide better targeted hydrophilic drug delivery systems.     

Short-time dynamics of partial wetting

When a liquid drop contacts a wettable surface, the liquid spreads over the solid to minimize the total surface energy. The first moments of spreading tend to be rapid. For example, a millimeter-sized water droplet will wet an area having the same diameter as the drop within a millisecond. For perfectly wetting systems, this spreading is inertially dominated. Here we identify that even in the presence of a contact line, the initial wetting is dominated by inertia rather than viscosity. We find that the spreading radius follows a power-law scaling in time where the exponent depends on the equilibrium contact angle. We propose a model, consistent with the experimental results, in which the surface spreading is regulated by the generation of capillary waves.     

Analytical selenoamino acid studies by chromatography with interfaced atomic mass spectrometry and atomic emission spectral detection

Consumption of selenium enriched plants or yeast-based nutritional supplements has been reported to provide anticarcinogenic benefits which are selenium compound dependent. Separation and identification of these selenium compounds is critical to understand the activity. Plants and yeast convert inorganic selenium in the soil or growth media into organoselenium compounds, probably following a route similar to the sulfur assimilatory pathway. Non-volatile selenium compounds produced include selenoamino acids, some of which have shown anticarcinogenic activity. Volatile compounds produced by chemical reaction of involatile precursors have also been found. An ion pair chromatographic method with ICP-MS detection for the separation of selenoamino acid standards potentially present in real samples is given. The method allows separation of selenoamino acids including such analytes as the cis-trans isomers of Se-1-propenyl-dl-selenocysteine. The method also provides the capability of determining the presence of selenoxides and possibly selenones, and tracking of other functionalities and reactions by selective derivatization. Alternatively, selenoamino acids are treated with ethylchloroformate to produce stable volatile derivatives which are amenable to GC separation with element specific atomic emission detection (GC-AED). Results of total selenium determination and speciation of selenium enriched yeast-based nutritional supplements, selenium enriched allium vegetables and bioremediation samples are presented.     

Convergence behavior of a new DSMC algorithm

The convergence rate of a new direct simulation Monte Carlo (DSMC) method, termed “sophisticated DSMC”, is investigated for one-dimensional Fourier flow. An argon-like hard-sphere gas at 273.15 K and 266.644 Pa is confined between two parallel, fully accommodating walls 1 mm apart that have unequal temperatures. The simulations are performed using a one-dimensional implementation of the sophisticated DSMC algorithm. In harmony with previous work, the primary convergence metric studied is the ratio of the DSMC-calculated thermal conductivity to its corresponding infinite-approximation Chapman–Enskog theoretical value. As discretization errors are reduced, the sophisticated DSMC algorithm is shown to approach the theoretical values to high precision. The convergence behavior of sophisticated DSMC is compared to that of original DSMC. The convergence of the new algorithm in a three-dimensional implementation is also characterized. Implementations using transient adaptive sub-cells and virtual sub-cells are compared. The new algorithm is shown to significantly reduce the computational resources required for a DSMC simulation to achieve a particular level of accuracy, thus improving the efficiency of the method by a factor of 2.     

Flexibility and lengths of bis-peptide nanostructures by electron spin resonance

We demonstrate the use of electron spin resonance (ESR) to determine long-range distances and flexibility in water-soluble bis-peptide molecular rods. Bis-peptide oligomers with 4-8 monomer units were synthesized. ESR determined that the end-to-end length of the peptides is linearly proportional to the number of monomers. The linear shape is, therefore, easily interpreted from the data. In addition, the flexibility of the rods was quantified directly from the ESR-determined distance distribution functions. Quantitative information on chain length and flexibility is important to develop the use of these oligomers as rodlike structural elements for applications such as bivalent display of ligands and as elements of future nanoscale devices.     

Spectroscopic analysis of bacterial biological warfare simulants and the effects of environmental conditioning on a bacterial spectrum

The ability to distinguish bacteria from mixed samples is of great interest, especially in the medical and defence arenas. This paper reports a step towards the aim of differentiating pathogenic endospores in situ, to aid any required response for hazard management using infrared spectroscopy combined with multivariate analysis. We describe a proof-of-principle study aimed at discriminating biological warfare simulants from common environmental bacteria. We also report an evaluation of multiple pre-processing techniques and subsequent differences in cross-validation of two pattern recognition models (Support Vector Machines and Principal Component–Linear Discriminant Analysis) for a six-class classification (bacterial classification). These classifications were possible with an average sensitivity of 88.0 and 86.9?%, and an average specificity of 97.6 and 97.5?% for the SVM and the PC-LDA models, respectively. Most spectroscopic models are built upon spectra from bacteria that have been specifically prepared for analysis by a particular method; this paper will comment upon the differences in the bacterial spectrum that occur between specific preparations when the bacteria have spent 30?days in the simulated weather conditions of a hot dry climate.

Line shape distortion effects in infrared spectroscopy

This paper explores different phenomena that cause distortions of infrared absorption spectra by mixing of reflective and absorptive band shape components of infrared spectra, and the resulting distortion of observed band shapes. In the context of this paper, we refer to the line shape of the variations of the refractive index in spectral regions of an absorption maximum (i.e., in regions of "anomalous dispersion") as "dispersive" or "reflective" line shape contributions, in analogy to previous spectroscopic literature. These distortions usually result in asymmetric bands with a negative intensity contribution at the high wavenumber of the band, accompanied by a shift toward lower wavenumber, and confounded band intensities. In extreme cases of band distortions caused by the "resonance Mie" (RMie) mechanism, spectral peaks may be split into doublets of peaks, change from positive to negative peaks, or appear as derivative-shaped features.     

Insulator, semiclassical oscillations and quantum Hall liquids at low magnetic fields

Magneto-transport measurements are performed on two-dimensional GaAs electron systems to probe the quantum Hall (QH) effect at low magnetic fields. Oscillations following the Shubnikov-de Haas (SdH) formula are observed in the transition from the insulator to QH liquid when the observed almost temperature-independent Hall slope indicates insignificant interaction correction. Our study shows that the existence of SdH oscillations in such a transition can be understood based on the non-interacting model.