Modeling a halogen dance reaction mechanism: A density functional theory study

Since the discovery of the halogen dance (HD) reaction more than 60 years ago, numerous insights into the mechanism have been unveiled. To date however, the reaction has not been investigated from a theoretical perspective. Density functional theory (DFT) was used to model the potential energy surface linking the starting reagents to the lithiated products for each step in the mechanism using a thiophene substrate. It was found that the lithium‐halogen exchange mechanism is critical to understand the HD mechanism in detail and yielded the knowledge that S_N2 transition states (TS) are favored over the four‐center type for the lithium‐bromine exchange steps. The overall driving force for the HD is thermodynamics, while the kinetic factors tightly control the reaction path through temperature. The S_N2 lithium‐bromide TS are barrierless, except the second, which is the limiting step. Finally, the model for the HD is discovered to be a pseudo‐clock type, due to a highly favorable bromide catalysis step and the reformation of 2‐bromothiophene. © 2016 Wiley Periodicals, Inc.     

Evaluating the performance of sampling plans to detect fumonisin B1 in maize lots marketed in Nigeria

Fumonisins are toxic and carcinogenic compounds produced by fungi that can be readily found in maize. The establishment of maximum limits for fumonisins requires the development of scientifically based sampling plans to detect fumonisin in maize. As part of an International Atomic Energy Agency effort to assist developing countries to control mycotoxin contamination, a study was conducted to design sampling plans to detect fumonisin in maize produced and marketed in Nigeria. Eighty-six maize lots were sampled according to an experimental protocol in which an average of 17 test samples, 100 g each, were taken from each lot and analyzed for fumonisin B1 by using liquid chromatography. The total variability associated with the fumonisin test procedure was measured for each lot. Regression equations were developed to predict the total variance as a function of fumonisin concentration. The observed fumonisin distribution among the replicated-sample test results was compared with several theoretical distributions, and the negative binomial distribution was selected to model the fumonisin distribution among test results. A computer model was developed by using the variance and distribution information to predict the performance of sampling plan designs to detect fumonisin in maize shipments. The performance of several sampling plan designs was evaluated to demonstrate how to manipulate sample size and accept/reject limits to reduce misclassification of maize lots.     

Magnesium iodide–4,4′‐bipyridine–water (1/3/4) and strontium iodide–4,4′‐bipyridine–propan‐1‐ol (1/2.5/2)

Both of the title compounds, catena‐poly­[[[tetra­aqua­magnesium(I)]‐μ‐4,4′‐bi­pyridine‐κ²N:N′] diiodide bis(4,4′‐bi­pyridine) solvate], {[Mg(C₁₀H₈N₂)(H₂O)₄]I₂·2C₁₀H₈N₂}_n, (I), and catena‐poly­[[[μ‐4,4′‐bi­pyridine‐bis­[di­iodo­bis­(propan‐1‐ol)­strontium(I)]]‐di‐μ‐4,4′‐bi­pyridine‐κ⁴N:N′] bis(4,4′‐bi­pyri­dine) solvate], {[Sr₂I₄(C₁₀H₈N₂)₃(C₃H₈O)₄]·2C₁₀H₈N₂}_n, (II), are one‐dimensional polymers which are single‐ and double‐stranded, respectively, the metal atoms being linked by the 4,4′‐bi­pyridine moieties. The Mg complex, (I), is [cis‐{(H₂O)₄Mg(N‐4,4′‐bi­pyridine‐N′)_(2/2)}]_(∞|∞)I₂·4,4′‐bi­pyridine and Mg has a six‐coordinate quasi‐octahedral coordination environment. The Sr complex, (II), is isomorphous with its previously defined Ba counterpart [Kepert, Waters & White (1996). Aust. J. Chem. 49 , 117–135], being [(propan‐1‐ol)₂I₂Sr(N‐4,4′‐bi­pyridine‐N′)_(3/2)]_(∞|∞)·4,4′‐bi­pyridine, with the I atoms trans‐axial in a seven‐coordinate pentagonal–bipyramidal Sr environment.     

Stable photogenerated carriers in magnetic semiconductor nanocrystals

We report the preparation and investigation of charged colloidal Co2+:ZnO and Mn2+:ZnO nanocrystals. Although both charged and magnetically doped colloidal semiconductor nanocrystals have been reported previously, colloidal charged and magnetically doped semiconductor nanocrystals as described herein have not. Conduction band electrons were introduced into colloidal ZnO diluted magnetic semiconductor (DMS) nanocrystals photochemically, and the resulting TM2+-e-CB interactions were observed by electron paramagnetic resonance spectroscopy (TM2+ = Co2+ or Mn2+). This new motif of colloidal charged magnetic semiconductor nanocrystals reveals attractive new opportunities for studying spin effects in DMS nanostructures relevant to proposed spintronics technologies.     

Vapor–Liquid Jump Conditions within a Porous Medium: Results for Mass and Energy

In this paper, we develop the mass and energy jump conditions for a vapor–liquid boundary within a porous medium. The analysis is restricted to a single fluid component and leads to the appropriate jump conditions for an evaporation front. The condition of local thermal equilibrium is assumed to exist in the homogeneous liquid and vapor regions, but not in the boundary region where rapid changes in the saturation occur.     

Dispersion in Heterogeneous Porous Media: One-Equation Non-equilibrium Model

In this paper, the method of large-scale averaging is used to develop two different one-equation models describing dispersion in heterogeneous porous media. The first model represents the case of large-scale mass equilibrium, while the second represents the asymptotic behavior of a two-equation model obtained by large-scale averaging. It is shown that a one-equation, non-equilibrium model can be developed even when the intrinsic large-scale averaged concentrations for each region are not equal. The solution of this non-equilibrium model is equivalent to the asymptotic behavior of the two-equation model.     

Modulation bandwidth and noise limit of photoconductive gates

The modulation bandwidth and noise limit of a photoconductive sampling gate are studied by reducing the parasitic capacitance and leakage current of the sampling circuit using an integrated junction field-effect transistor (JFET) source follower. The modulation bandwidth of the photoconductive sampling gate is limited by the external parasitic capacitance, and its efficiency is found to saturate at a laser gating power of about 1 mW. It is determined that the noise of the photoconductive sampling gate is dominated by the photovoltaic current due to the gating laser amplitude fluctuation. A minimum noise level of 4 nV Hz^–1/2 has been measured, and an enhancement in signal-to-noise ratio by a factor of >45 has been achieved after the integration of the source follower with the photoconductive sampling gate. The JFET source follower serves to increase the modulation bandwidth of the photoconductive sampling gate by about 15 times and buffer the charge of the measured signal using its extremely high gate input impedance. The performance of the photoconductive sampling gate in regard to invasiveness and gating efficiency has been optimized, while a picosecond temporal resolution has been maintained and the signal-to-noise performance has been enhanced using a gating laser power as low as 10 W.     

Subcellular localization patterns and their relationship to photodynamic activity of pyropheophorbide-a derivatives

To determine if subcellular localization is important to photodynamic therapy (PDT) efficacy, an in vitro fluorescence microscopy study was conducted with a congeneric series of pyropheophorbide-a derivatives in human pharyngeal squamous cell carcinoma (FaDu) cells and murine radiation-induced fibrosarcoma (RIF) mutant cells. In the FaDu cells the octyl, decyl and dodecyl ether derivatives localized to the lysosomes at extracellular concentrations less than needed to produce a 50% cell kill (LD50). At extracellular concentrations equal or greater than the LD50 the compounds localized mainly to mitochondria. The propyl, pentyl, hexyl and heptyl ether derivatives localized mainly to the mitochondria at all concentrations studied. This suggested that mitochondria are a sensitive PDT target for these derivatives. Similar experiments were performed with two Photofrin-PDT resistant RIF cell lines, one of which was found to be resistant to hexyl ether derivative (C6) mediated-PDT and the other sensitive to C6-PDT relative to the parent line. At extracellular concentrations of C6 below the LD50 of each cell line, the mutants exhibited lysosomal localization. At concentrations above these values the patterns shifted to a mainly mitochondrial pattern. In these cell lines mitochondrial localization also correlated with PDT sensitivity. Localization to mitochondria or lysosomes appeared to be affected by the aggregation state of the congeners, all of which are highly aggregated in aqueous medium. Monomers apparently were the active fraction of these compounds because equalizing the extracellular monomer concentrations produced equivalent intracellular concentrations, photoxicity and localization patterns. Compounds that were mainly aggregates localized to the lysosomes where they were rendered less active. Mitochondria appear to be a sensitive target for pyropheophorbide-a-mediated photodamage, and the degree of aggregation seems to be a determinant of the localization site.