Characterization of chemical selectivity in micellar electrokinetic chromatography. VI. Effects of surfactant counter-ion

Linear solvation energy relationships and free energy of transfer data were used to evaluate the influence of the surfactant counter-ion on selectivity in micellar electrokinetic chromatography. It was determined that selectivity differences are dependent on the valency of the counter-ion but not the type of counter-ion. Monovalent surfactants, sodium dodecyl sulfate (SDS) and lithium dodecyl sulfate, have nearly identical selectivity behavior. The divalent surfactants, magnesium didodecyl sulfate and copper didodecyl sulfate also show very similar behavior. However, when the divalent counter-ion species is compared to SDS under similar conditions, significant differences are observed. Most notably, the utilization of divalent counter-ion species of dodecyl sulfate surfactants causes the micelles to become more hydrophobic and a weaker hydrogen bond donating pseudo-stationary phases. It is believed that the divalent counter-ions reduce the electrostatic repulsion between the surfactant head groups and therefore, increase the chain packing of the monomers in the micelle aggregates. This reduces the degree of hydration of the micellar palisade layer leading to a decreased ability of the micelle to participate in polar/polarizable and hydrogen bonding interactions with solute molecules.     

Validation of a Monte Carlo HPGe detector model against irradiated foil gamma-ray spectroscopy measurements

In order to separate and pre-concentrate uranium from aqueous phase, a novel silica-based adsorbent was prepared by impregnating nalidixic acid (HNA) into a macroreticular silica/polymer composite support (SiO₂-P) with a mean diameter of 60 μm. Adsorption behavior of uranium from aqueous solution onto the adsorbent was studied. Experimental results indicated that HNA/SiO₂-P showed strong adsorption for uranium in a wide range of pH from 3.5 to 10.0, and the maximum adsorption capacity was 35.4 mg g⁻¹. In addition, HNA/SiO₂-P exhibited good selectivity for U(VI) and showed weak or bare adsorption affinity to foreign ions. Kinetic and isotherm of uranium adsorption were in accordance with the pseudo-second-order kinetic model and Langmuir isotherm adsorption model, respectively. Moreover, U(VI) sorption was found to be an endothermic reaction and spontaneous under experimental state. The synthesized adsorbent showed an admirable stability at lower pH values in aqueous solution.

     

Comparison of irradiated foil measurements with activation calculations and HPGe simulations

Theoretical activation calculations for Fe, Ni, and stainless steel foils were compared against irradiated foil measurements from a critical assembly. Calculated/experiment values spanning 0.62–1.31 showed that the restricted approach used here is insufficient for experiment planning, with the collapsed cross-section being the primary source of error. The effect of decay time on gamma-ray spectroscopy measurement reliability was investigated using a Monte Carlo HPGe detector model. Simulations showed no correlation with decay time, absent interferences. Specific interferences for Fe-59 (Ni) and Co-60 (stainless steel) activation product ratios suggested optimal measurement windows having respective decay times of 9–11 days and 4–7 days.     

Magnetic properties of stainless steels at room and cryogenic temperatures

The magnetic properties of ten types of ferritic and martensitic stainless steels have been measured at room temperature and at 77 K. The steel samples studied were in the annealed state as received from the manufacturer. Our room temperature measurements indicate significantly harder magnetic properties than those quoted in the ASM International Handbook, which studied fully annealed stainless steel samples. Despite having harder magnetic properties than fully annealed steels some of the as-received steels still display soft magnetic properties adequate for magnetic applications. The carbon content of the steels was found to affect the permeability and coercive force, with lower-carbon steels displaying significantly higher permeability and lower coercive force. The decrease in coercive force with reduced carbon content is attributed to fewer carbide inclusions which inhibit domain wall motion. Cooling to 77 K resulted in harder magnetic properties. Averaged over the ten steels tested the maximum permeability decreased by 8%, the coercive force increased by 14%, and the residual and saturation flux densities increased by 4% and 3%, respectively. The change in coercive force when cooled is comparable to the theoretical prediction for iron, based on a model of domain wall motion inhibited by inclusions. The modest changes of the magnetic properties indicate that the stainless steels can still be used in magnetic applications at very low temperatures.     

Spectrophotometric determination and computational evaluation of the rates of hydrolysis of 9-amino-substituted acridines

Aminoacridines have a long history in the drug and dye industries and display a wide range of biological and physical properties. Despite the historical relevance of 9-aminoacridines, there have been few studies investigating their stability. 9-Aminoacridines are known to hydrolyze at the C9-N15 bond, yielding acridones. In this study, the pH-dependent hydrolysis rates of a series of 9-substituted aminoacridines are investigated. In addition, ground-state physical properties of the compounds are determined using ab initio quantum mechanics calculations to gain insight into the forces that drive hydrolysis. An analysis of the bond orders, bond dissociation energies, and conformational energies show that the rate of hydrolysis depends on two main factors: delocalization across the C9-N15 bond and steric effects. The computational results are applied to explain the change in experimental rates of hydrolysis going from primary to secondary and to tertiary substituted 9-aminoacridines. In the case of tertiary substituted amines, the calculations indicate the C9-N15 bond is forced into a more gauche-like conformation, greatly diminishing delocalization (as shown by reductions in bond orders and bond energy), which leads to rapid hydrolysis. A model of intramolecular hydrogen bonding is also presented, which explains the increased rate of hydrolysis observed for highly substituted compounds under acidic conditions.     

Discrimination of non-native consonant contrasts varying in perceptual assimilation to the listener's native phonological system

Classic non-native speech perception findings suggested that adults have difficulty discriminating segmental distinctions that are not employed contrastively in their own language. However, recent reports indicate a gradient of performance across non-native contrasts, ranging from near-chance to near-ceiling. Current theoretical models argue that such variations reflect systematic effects of experience with phonetic properties of native speech. The present research addressed predictions from Best's perceptual assimilation model (PAM), which incorporates both contrastive phonological and noncontrastive phonetic influences from the native language in its predictions about discrimination levels for diverse types of non-native contrasts. We evaluated the PAM hypotheses that discrimination of a non-native contrast should be near-ceiling if perceived as phonologically equivalent to a native contrast, lower though still quite good if perceived as a phonetic distinction between good versus poor exemplars of a single native consonant, and much lower if both non-native segments are phonetically equivalent in goodness of fit to a single native consonant. Two experiments assessed native English speakers' perception of Zulu and Tigrinya contrasts expected to fit those criteria. Findings supported the PAM predictions, and provided evidence for some perceptual differentiation of phonological, phonetic, and nonlinguistic information in perception of non-native speech. Theoretical implications for non-native speech perception are discussed, and suggestions are made for further research.     

Synthesis and reactivity of bicyclo[3.2.1]octanoid-derived cyclopropanes

Photochemical oxa-di-π-methane rearrangement of bicyclo[3.2.1]octanoid scaffolds affords multifunctional, donor-acceptor cyclopropanes. A related photochemical reaction of an iminium ether substrate uncovered an unprecedented aza-di-π-methane rearrangement of a β,γ-unsaturated iminium. Donor-acceptor cyclopropanes have been evaluated as substrates for reactions generating several new chemotypes.     

Effects of hot water extraction and fungal decay on wood crystalline cellulose structure

The effect of hot-water extraction and two types of fungal decay, brown rot and white rot, on wood crystalline cellulose structure was examined using a combination of X-ray diffraction (XRD) and ¹³C solid-state nuclear magnetic resonance (NMR) spectroscopy. Although having opposite effects on the overall crystallinity of the wood, the XRD results revealed that both extraction and brown-rot decay caused a significant decrease in the 200 crystal plane spacing (d-spacing) not seen for the white-rotted samples. This effect was found to be additive, as samples that were first extracted, then decayed showed a double decrease in d-spacing compared to that caused by extraction alone. This suggested that, despite having a similarly directed effect on the spacing of the crystalline planes, the two treatment methods facilitate a decrease in d-spacing in different ways. NMR results support the conclusion of differing structural effects, suggesting that the hot-water extraction procedure was causing a co-crystallization of existing crystalline domains, while the brown rot decay was depolymerizing the cellulose chains of the crystals, possibly allowing the remaining crystalline material the freedom to relax into a more energetically favorable, tightly packed state. These findings could have important implications for those seeking to understand the effects of modification treatments or biodegradation of crystalline cellulose nanostructures in their native states.     

Serine-cis-proline and serine-trans-proline isosteres: stereoselective synthesis of (Z)- and (E)-alkene mimics by Still-Wittig and Ireland-Claisen rearrangements

Two new amide isosteres of Ser-cis-Pro and Ser-trans-Pro dipeptides were designed and stereoselectively synthesized to be incorporated into potential inhibitors of the phosphorylation-dependent peptidylprolyl isomerase Pin1, an essential regulator of the cell cycle. The cis mimic, the (Z)-alkene isomer, was formed through the use of a Still-Wittig [2,3]-sigmatropic rearrangement, while the trans mimic, the (E)-alkene, was synthesized through the use of an Ireland-Claisen [3,3]-sigmatropic rearrangement. Starting from N-Boc-Ser(OBn)-N(OMe)Me, both mimics were synthesized in Boc-protected form suitable for peptide synthesis with an overall yield of 20% in 10 steps for the cis mimic and 13% in eight steps for the trans mimic.