Surface composition of PdCuAu ternary alloys: a combined LEIS and XPS study

PdCuAu ternary alloy samples with different composition were synthesized on top of ZrO₂‐modified porous stainless steel disks by the sequential electroless deposition technique. The structure, morphology and bulk composition of the samples were characterized by X‐ray diffraction (XRD), scanning electron microscopy and energy dispersive X‐ray spectroscopy (EDX). Complete alloy formation with a pure fcc phase for the Pd₇₁Cu₂₆Au₃, Pd₇₀Cu₂₅Au₅ and Pd₆₇Cu₂₄Au₉ samples and a bcc structure for the Pd₆₂Cu₃₆Au₂ and Pd₆₀Cu₃₇Au₃ samples were obtained upon annealing at 500 °C for 120 h as revealed by XRD. A combination of low‐energy ion scattering (LEIS) and X‐ray photoelectron spectroscopy (XPS) was used to investigate the surface properties of the PdCuAu alloys. XPS results confirmed alloy formation under the annealing conditions. XPS analysis also revealed that the near‐surface regions of the alloys became enriched in Pd with respect to the bulk composition determined by EDX. In contrast, LEIS and angle‐resolved XPS analyses showed that the top‐most surface layers in all samples were copper‐rich compared with the bulk composition. This high Cu surface concentration could impart resistance to bulk sulfide formation to the PdCuAu alloy membranes. Copyright © 2015 John Wiley & Sons, Ltd.     

Potential of prodendronic polyamines with modulated segmental charge density as novel coating for fast and efficient analysis of peptides and basic proteins by CE and CE‐MS

In this work, the suitability of a new polymer family has been investigated as capillary coatings for the analysis of peptides and basic proteins by CE. This polymer family has been designed to minimize or completely prevent protein–capillary wall interactions and to modify the EOF. These coating materials are linear polymeric chains bearing as side cationizable moiety a dentronic triamine derived from N,N,N’,N’‐tetraethyldiethylenetriamine (TEDETA), which is linked to the backbone through a spacer (unit labeled as TEDETAMA). Four different polymers have been prepared and evaluated: a homopolymer which comprised only of those cationizable repetitive units of TEDETAMA, and three copolymers that randomly incorporate TEDETAMA together with neutral hydrosoluble units of N‐(2‐hydroxypropyl) methacrylamide (HPMA) at different molar percentages (25:75, 50:50 and 75:25). It has been demonstrated that the composition of the copolymers influences the EOF and therefore the separation of the investigated biopolymers. Among the novel polymers studied, poly‐(TEDETAMA‐co‐HPMA) 50:50 copolymer was successfully applied as coating material of the inner capillary surface in CE‐UV and CE‐MS, providing EOF reversing together with fast and efficient baseline separation of peptides and basic proteins. Finally, the feasibility of the polymer‐coated capillary was shown through the analysis of lysozyme in a cheese sample.     

A Safety Strategy for Producing Poly(Acrylic Acid) of Low Molar Mass

The synthesis of poly(acrylic acid) (PAA) of low molar mass under safe conditions is difficult due to the high polymerization rate of acrylic acid (AA) and the fast heat generation. The aqueous‐solution “semibatch” polymerization of non‐ionized AA in almost starved conditions involves high initiator loads when low molar masses are required. This article proposes the simultaneous feeding of AA and nonconventional chain transfer agents (CTA) as a strategy aimed at controlling both the molar masses and the generated heat rate. Three CTAs are investigated: 2‐mercaptoethanol, thioglycolic acid, and isopropyl alcohol. Even when PAA of relatively low molar mass can be produced by adequately selecting the flow rates and concentrations of both AA and CTA, it is found that the nature of CTA can have a significant effect on the polymerizations kinetics. The mechanisms responsible for these effects are discussed with the help of a representative mathematical model.

     

Symmetry and the golden ratio in the analysis of a regular pentagon

The regular pentagon had a symbolic meaning in the Pythagorean and Platonic philosophies and a subsequent important role in Western thought, appearing also in arts and architecture. A property of regular pentagons, which was probably discovered by the Pythagoreans, is that the ratio between the diagonal and the side of these pentagons is equal to the golden ratio. Here, we will study some relations existing between a regular pentagon and this ratio. First, we will focus on the group of fivefold rotational symmetry, to find the position in the complex plane of the vertices of this geometric figure. Then, we will propose an analytic method to solve the same problem based on the Cartesian coordinates, a method where we find the golden ratio without any specific geometric consideration. This study shows a comparison of the use of complex numbers, symmetries and analytic methods, applied to a subject which can be interesting for general education in mathematics. In fact, the proposed approach can convey and link several concepts, requiring only a general pre-college education, showing at the same time the richness that mathematics can offer in solving geometric problems.     

Analysis of chiral amino acids in cerebrospinal fluid samples linked to different stages of Alzheimer disease

Chiral micellar electrokinetic chromatography with laser-induced fluorescence detection (chiral-MEKC-LIF) was used to investigate D- and L-amino acid contents in cerebrospinal fluid (CSF) samples related to different Alzheimer disease (AD) stages. CSF samples were taken from (i) control subjects (S1 pool), (ii) subjects showing a mild cognitive impairment who remained stable (S2 pool), (iii) subjects showing an mild cognitive impairment that progressed to AD (S3 pool) and (iv) subjects diagnosed with AD (S4 pool). The optimized procedure only needed 10 μL of CSF and it included sample cleaning, derivatization with FITC and chiral-MEKC-LIF separation. Eighteen standard amino acids were baseline separated with efficiencies up to 703,000 plates/m, high sensitivity (LODs in the nM range) and good resolution (values ranging from 2.6 to 9.5). Using this method, L-Arg, L-Leu, L-Gln, γ-aminobutyric acid, L-Ser, D-Ser, L-Ala, Gly, L-Lys, L-Glu and L-Asp were detected in all the CSF samples. S3 and S4 samples (i.e. AD subjects) showed significant lower amounts of L-Arg L-Lys, L-Glu and L-Asp compared to the non-AD S1 and S2 samples, showing in the S4 group the lowest amounts of L-Arg L-Lys, L-Glu and L-Asp. Moreover, γ-aminobutyric acid was significantly higher in AD subjects with the highest amount also found for S4. No significant differences were observed for the rest of amino acids including D-Ser. Based on the obtained chiral-MEKC-LIF data, it was possible to correctly classify all the samples into the four groups. These results demonstrate that the use of enantioselective procedures as the one developed in this work can provide some new light on the investigations of AD, including the discovery of new biomarkers related to different stages of AD.     

A comparison of depletion versus equalization for reducing high-abundance proteins in human serum

In this work three methods to diminish the content of most highly abundant proteins in human serum have been studied and compared. Protein depletion with ACN or DTT and protein equalization with the ProteoMiner^? (PM) have been assessed by 1‐D gel electrophoresis and MS. After treatment 5, 18 and 9 major proteins within the 20 most abundant proteins in serum were identified for the ACN, DTT and PM methods, respectively. The ACN method was efficient for depleting high molecular weight proteins, over 75 KDa, resulting in 10±4% (n=3) of the total protein content remaining in the depleted serum. In addition, 75% of the proteins belonging to the group of the 20 most abundant proteins were not detected, making this depletion strategy a cheap alternative to expensive commercial tools regularly used for removing high abundance proteins from serum. The ACN extract was found rich in apolipoproteins. The dithithreitol method promotes the precipitation of proteins rich in disulfide bonds, mainly albumin, with 73±7% (n=3) of the total protein content remaining in the depleted serum, which was found rich in immunoglobulins. The PM method compresses the dynamic range of the serum proteins, rendering an extract containing 16±2% (n=3) of the total initial protein content. The extract was found to be rich in both apolipoproteins and immunoglobulins. As a general rule the DTT and PM methods provide a compression of the dynamic range of serum protein concentrations while the ACN method allows an effective depletion of the protein fraction above 72 KDa.     

Extending the GC-SAFT-VR approach to associating functional groups: Alcohols, aldehydes, amines and carboxylic acids

The statistical associating fluid theory is a widely used molecular-based equation of state that has been successfully applied to study a broad range of fluid systems. It provides a framework in which the effects of molecular shape and interactions on the thermodynamics and phase behavior of fluids can be separated and quantified. In the original approach, molecules were modeled as chains composed of identical segments; the heterogeneity of molecules in terms of structure and functional groups was described implicitly through effective parameters. To overcome this limitation, in recent works [Peng et al. Fluid Phase Equilib. 227(2), 131 (2009); Ind. Eng. Chem. Res. 49(3), 1378 (2010)] the GC-SAFT-VR approach has been developed to extend the theory to model chains composed of segments of different size and/or energy of interaction and enable the development of a group-contribution approach within the SAFT-VR framework in which molecular heterogeneity and connectivity is explicitly accounted for. The parameters for several key functional groups (CH₃, CH₂, CH, CH₂CH, CO, C₆H₅, esters, ethers, cis-alkenes and trans-alkenes groups) were determined by fitting to experimental vapor pressure and saturated liquid density data for a number of small molecules containing the functional groups of interest and transferability of the parameters tested by comparing the theoretical predictions with experimental data for pure fluids not included in the fitting process and binary mixtures of both simple fluids and the VLE and LLE of small molecules in polymer systems. In this work, we further extend the applicability of the GC-SAFT-VR approach through the study of the vapor-liquid phase behavior of associating systems, such as linear and branched alcohols, primary and secondary amines, aldehydes, and carboxylic acids, and their mixtures. In the study of these new molecules several new functional groups (OH (linear and branched), HCO, NH₂, NH and COOH) are defined and their molecular parameters characterized. The transferability of the parameters is again tested by comparing the theoretical predictions with experimental data for pure fluids and binary mixtures not included in the fitting process. The GC-SAFT-VR approach is found to predict the phase behavior of the systems studied in most cases in good agreement with experimental data and accurately captures the effects of changes in structure and molecular composition on phase behavior.     

Tuning high aqueous phase uptake in nonionic water-in-oil microemulsions for the synthesis of Mn-Zn ferrite nanoparticles: phase behavior, characterization, and nanoparticle synthesis

In this work, the formation of water-in-oil (w/o) microemulsions with high aqueous phase uptake in a nonionic surfactant system is investigated as potential media for the synthesis of Mn-Zn ferrite nanoparticles. A comprehensive study based on the phase behavior of systems containing precursor salts, on one hand, and precipitating agent, on the other hand, was carried out to identify key regions on (a) pseudoternary phase diagrams at constant temperature (50 °C), and (b) pseudobinary phase diagrams at constant surfactant (S):oil(O) weight ratio (S:O) as a function of temperature. The internal structure and dynamics of microemulsions were studied systematically by conductivity and self-diffusion coefficient determinations (FT PGSE (1)H NMR). It was found that nonpercolated w/o microemulsions could be obtained by appropriate tuning of composition variables and temperature, with aqueous phase concentrations as high as 36 wt % for precursor salts and 25 wt % for precipitating agent systems. Three compositions with three different dynamic behaviors (nonpercolated and percolated w/o, as well as bicontinuous microemulsions) were selected for the synthesis of Mn-Zn ferrites, resulting in nanoparticles with different characteristics. Spinel structure and superparamagnetic behavior were obtained. This study sets firm basis for a systematic study of Mn-Zn ferrite nanoparticle synthesis via different scenarios of microemulsion dynamics, which will contribute to a better understanding on the relationship of the characteristics of the obtained materials with the properties of the reaction media.     

1H NMR and UV-visible data fusion for determining Sudan dyes in culinary spices

Two data fusion strategies (variable and decision level) combined with a multivariate classification approach (Partial Least Squares-Discriminant Analysis, PLS-DA) have been applied to get benefits from the synergistic effect of the information obtained from two spectroscopic techniques: UV-visible and ¹H NMR. Variable level data fusion consists of merging the spectra obtained from each spectroscopic technique in what is called “meta-spectrum” and then applying the classification technique. Decision level data fusion combines the results of individually applying the classification technique in each spectroscopic technique. Among the possible ways of combinations, we have used the fuzzy aggregation connective operators. This procedure has been applied to determine banned dyes (Sudan III and IV) in culinary spices. The results show that data fusion is an effective strategy since the classification results are better than the individual ones: between 80 and 100% for the individual techniques and between 97 and 100% with the two fusion strategies.