Thermodynamics of multicomponent electrolyte solutions: Aqueous mixtures of two salts from among NaCl,KCl, NaH2PO4, and KH2PO4 at 25° C

Five of the six possible aqueous two-salt mixtures from among NaCl, KCl, NaH₂PO₄,and KH₂PO₄ have been studied by the isopiestic method at 25°C. The sixth mixture, NaCl–KCl, has been studied previously. The deviations from ideal mixing behavior are described by a series of coefficients which were found by regression analysis. The coefficients were used to calculate the excess Gibbs energies of mixing for equal ionic strength fractions of each salt and the trace activity coefficient of each salt at an ionic strength of 2 mode-kg^–1. The cross-square mixing rule is obeyed within experimental uncertainty for the excess Gibbs energies of mixing.     

Quantitative analysis of complex amino acids and RGD peptides by X‐ray photoelectron spectroscopy (XPS)

The C 1 s, N 1 s, and O 1 s core level binding energies (BEs) of the functional groups in amino acids (glycine, aspartic acid, glutamic acid, arginine, and histidine) with varied side‐chains and cell‐binding RGD‐based peptides have been determined and characterized by X‐ray photoelectron spectroscopy with a monochromatic Al K_α source. The zwitterionic nature of the amino acids in the solid state is unequivocally evident from the N 1 s signals of the protonated amine groups and the C 1 s signature of carboxylate groups. Significant adventitious carbon contamination is evident for all samples but can be quantitatively accounted for. No intrinsic differences in the XP spectra are evident between two polymorphs (α and γ) of glycine, indicating that the crystallographic differences have a minor influence on the core level BEs for this system. The two nitrogen centers in the imidazole group of histidine exhibit an N 1 s BE shift that is in line with previously reported data for theophylline and aqueous imidazole solutions, while the nitrogen and carbon chemical shifts reflect the unusual guanidinium chemical environment in arginine. It is shown that the complex envelopes of C 1 s and O 1 s photoemission spectra for short‐chain peptides can be analyzed quantitatively by reference to the less complex XP spectra of the constituent amino acids, provided the peptides are of high enough purity. The distinctive N 1 s photoemission from the amide linkages provides an indicator of peptide formation even in the presence of common impurities, and variations in the relative intensities of N 1 s were found to be diagnostic for each of the three peptides investigated (RGD, RGDS, and RGDSC). Copyright © 2013 John Wiley & Sons, Ltd.     

Influence of Cyclodextrins on the Kinetics of Oxidation of Amino Acids and BSA by Hydrazyl Radicals

The kinetics of oxidation of amino acids (Arg, His, Lys, Phe, Thr and Tyr), a dipeptide (Gly-His), and BSA (bovine serum albumin) by two persistent water soluble free radicals of the hydrazyl type has been studied.The rate decreases in the order Arg>Lys>Tyr>Thr>HisBSAPheGly-His with bothfree radicals. Addition to the reaction mixture of - and -cyclodextrin decreases the oxidation rate, probably due to amino acidencapsulation in the cyclodextrin cavity. -Cyclodextrin protects more efficiently against oxidation than -cyclodextrin.     

Electronic Structures of Wurtzite GaN with Ga and N Vacancies

The electronic band structures of wurtzite GaN with Ga and N vacancy defects are investigated by means of the first-principles total energy calculations in the neutral charge state. Our results show that the band structures can be significantly modified by the Ga and N vacancies in the GaN samples. Generally, the width of the valence band is reduced and the band gap is enlarged. The defect-induced bands can be introduced in the band gap of GMV due to the Ga and N vacancies. Moreover, the GaN with high density of N vacancies becomes an indirect gap semiconductor. Three defect bands due to Ga vacancy defects are created within the band gap and near the top of the valence band. In contrast, the N vacancies introduce four defect bands within the band gap. One is in the vicinity of the top of the valence band, and the others are near the bottom of the conduction band. The physical origin of the defect bands and modification of the band structures due to the Ga and N vacancies are analysed in depth.     

A new acetonitrile-free mobile phase method for LC-ELSD quantification of fructooligosaccharides in onion (Allium cepa L.)

Onion soluble non-structural carbohydrates consist of fructose, glucose and sucrose plus fructooligosaccharides (FOS) with degrees of polymerisation (DP) in the range of 3-19. In onion, sugars and FOS are typically separated using liquid chromatography (LC) with acetonitrile (ACN) as a mobile phase. In recent times, however, the production of ACN has diminished due, in part, to the current worldwide economic recession. A study was therefore undertaken, to find an alternative LC method to quantify sugars and FOS from onion without the need for ACN. Two mobile phases were compared; the first taken from a paper by Vågen and Slimestad (2008) [3] using ACN mobile phase, the second, a newly reported method using ethanol (EtOH). The EtOH mobile phase eluted similar concentrations of all FOS compared to the ACN mobile phase. In addition, limit of detection, limit of quantification and relative standard deviation values were sufficiently and consistently lower for all FOS using the EtOH mobile phase. The drawback of the EtOH mobile phase was mainly the inability to separate all individual sugar peaks, yet FOS could be successfully separated. However, using the same onion extract, a previously established LC method based on an isocratic water mobile phase could be used in a second run to separate sugars. Although the ACN mobile phase method is more convenient, in the current economic climate a method based on inexpensive and plentiful ethanol is a valid alternative and could potentially be applied to other fresh produce types.In addition to the mobile phase solvent, the effect of extraction solvents on sugar and FOS concentration was also investigated. EtOH is still widely used to extract sugars from onion although previous literature has concluded that MeOH is a superior solvent. For this reason, an EtOH-based extraction method was compared with a MeOH-based method to extract both sugars and FOS. The MeOH-based extraction method was more efficacious at extracting sugars and FOS from onion flesh, eluting significantly higher concentrations of glucose, kestose, nystose and DP5-DP8.     

Development of tip-enhanced optical spectroscopy for biological applications: a review

Tip-enhanced optical spectroscopy is an approach that holds a good deal of promise for the nanoscale characterisation of matter. Tip-enhanced Raman spectroscopy (TERS) has been demonstrated on a variety of samples: inorganic, organic and biological. Imaging using TERS has been shown for carbon nanotubes due to their high scattering efficiency. There are a number of compelling motivations to consider alternative approaches for biological samples; most importantly, the potential for heat damage of biomolecules and long acquisition times. These issues may be addressed through the development of tip-enhanced coherent anti-Stokes Raman scattering microscopy.     

The microscopic investigation of structures of moving flux lines by neutron and muon techniques

We have used a variety of microscopic techniques to reveal the structure and motion of flux line arrangements, when the flux lines in low T _c type II superconductors are caused to move by a transport current. Using small-angle neutron scattering by the flux line lattice (FLL), we are able to demonstrate directly the alignment by motion of the nearest-neighbor FLL direction. This tends to be parallel to the direction of flux line motion, as had been suspected from two-dimensional simulations. We also see the destruction of the ordered FLL by plastic flow and the bending of flux lines. Another technique that our collaboration has employed is the direct measurement of flux line motion, using the ultra-high-resolution spectroscopy of the neutron spin-echo technique to observe the energy change of neutrons diffracted by moving flux lines. The muon spin rotation (μSR) technique gives the distribution of values of magnetic field within the FLL. We have recently succeeded in performing μSR measurements while the FLL is moving. Such measurements give complementary information about the local speed and orientation of the FLL motion. We conclude by discussing the possible application of this technique to thin film superconductors.     

Heat loss corrections for heat capacity flow calorimeters

A single equation describes all linear thermal models for the heat losses in heat capacity flow calorimeters. This equation is used to correct for heat losses by extrapolating the apparent heat capacity to the zero value of a modified reciprocal flow rate. The method, which does not require an auxiliary pump, has been successfully tested for aqueous sodium chloride solutions to 300.8°C, with the derived apparent molar heat capacities being in agreement with literature values. Aqueous solutions of 2-methylpropan-2-ol (t-butanol) gave anomalous results requiring further investigation. Two other correction methods are both consistent with the new method but apply less generally and require care in the evaluation of the correction factors.