Partial widths and branching ratios for the emitted electron resulting from interatomic Coulombic decay in quantum wells heterostructure

Interatomic coulomb decay (ICD) is a decay process relying on the Coulombic interaction between neighbouring atoms, molecules or nanostructures. Due to this process, an electron is emitted into the continuum. We study the ICD process in a system of the double quantum well heterostructure and investigate how we can manipulate the structure's parameters such that a better detection of the ICD's emitted electron is achieved. For this purpose, we calculated the partial widths (PWs) and branching ratios (BRs) of the ICD's emitted electron to the left and right asymptotes of the heterostructure; these will give an estimation of the detection current. We manipulated the structure's parameters and took into account the repulsion from the electron in the ground state located in the left well. By introducing two small barriers in the vicinity of the right QW, we observed a BR three times larger than in the structure without the barriers. We also investigate the effect of repulsion due to the second electron. This work gives a better understanding of the dynamics of the scattered ICD's electron, and realisation of better design rules for future experimental observation of ICD in nanostructures.     

Adsorption-Inhibition of Clathrate Hydrates by Self-Assembled Nanostructures

The mechanism by which safranine O (SFO), an ice growth inhibitor, halts the growth of single crystal tetrahydrofuran (THF) clathrate hydrates was explored using microfluidics coupled with cold stages and fluorescence microscopy. THF hydrates grown in SFO solutions exhibited morphology changes and were shaped as truncated octahedrons or hexagons. Fluorescence microscopy and microfluidics demonstrated that SFO binds to the surface of THF hydrates on specific crystal planes. Cryo-TEM experiments of aqueous solutions containing millimolar concentrations of SFO exhibited the formation of bilayered lamellae with an average thickness of 4.2±0.2 nm covering several μm². Altogether, these results indicate that SFO forms supramolecular lamellae in solution, which might bind to the surface of the hydrate and inhibit further growth. As an ice and hydrate inhibitor, SFO may bind to the surface of these crystals via ordered water molecules near its amine and methyl groups, similar to some antifreeze proteins.     

Electron spin resonance (ESR/EPR) of free radicals observed in human red hair: a new,simple empirical method of determination of pheomelanin/eumelanin ratio in hair

The definition of the concentration of pheomelanin in the skin is an issue of great interest because in the case of being influenced by UV radiation, it manifests itself as a prooxidant, causing various skin disorders including melanoma that might help to explain the relatively high incidence of skin cancer among individuals with red hair. The ESR spectra of red hair samples were investigated. It was found that at low microwave power, they are characterized by two types of spectra. Red hair ESR signals result from a superposition of two spectral shapes, a singlet spectrum as a result of the existence of eumelanin and a triplet spectrum as a result of the existence of pheomelanin. At high microwave power, only triplet spectra shape was detected, caused by saturation of the eumelanin singlet. Using different concentration ratios of black to red hair, we measured ESR spectra and plotted the ratio values in each sample against a measured ‘g‐factor’ (experimental). We found that there is a linear relationship between these two parameters. So, it is evident that using these results, the concentration ratio of pheomelanin to eumelanin in a sample of hair can be easily determined by an almost noninvasive method. This can be considered a potential advantage for many practical activities compared with other invasive methods. The concentration dependence curve of pheomelanin (µg/mg) on g_exp‐factor in an ESR spectrum of hair has been designed, which allows the determination of the amount of pheomelanin in hair of any color. Copyright © 2014 John Wiley & Sons, Ltd.     

In Silico Design of Heteroaromatic Half‐Sandwich RhI Catalysts for Acetylene [2+2+2] Cyclotrimerization: Evidence of a Reverse Indenyl Effect

A mechanistic density functional theory study of acetylene [2+2+2] cyclotrimerization to benzene catalyzed by Rh^I half metallocenes is presented. The catalyst fragment contains a heteroaromatic ligand, that is, the 1,2‐azaborolyl (Ab) or the 3a,7a‐azaborindenyl (Abi) anions, which are isostructural and isoelectronic to the hydrocarbon cyclopentadienyl (Cp) and indenyl (Ind) anions, respectively, but differ from the last ones on having two adjacent carbon atoms replaced with a boron and a nitrogen atom. The better performance of either the classic hydrocarbon or the heteroaromatic catalysts is found to depend on the different mechanistic paths that can be envisioned for the process. The present analyses uncover and explain general structure–reactivity relationships that may serve as rational design principles. In particular, we provide evidence of a reverse indenyl effect.     

Determination of primordial radionuclide concentrations in UAE groundwater using high-resolution gamma-ray spectrometry

Journal of Radioanalytical and Nuclear Chemistry - Groundwater is the most valuable resource in arid regions, such as UAE. Estimations of natural radionuclide concentrations are important to...     

Some metrological aspects of the comparison between two ordinal measuring systems

The usage of ordinal scales (sometimes called ‘semi-quantitative’ scales) for performing measurements in the area of applied chemical metrology and quality assurance is widespread. This paper presents a method for handling actions such as calibration, measuring systems’ capabilities comparison and reproducibility evaluation as a comparison between two measuring systems (MSs) referring to a known/unknown reference standard. The strength of the agreement between these MSs is evaluated through two known versions of Cohen’s kappa statistics (the traditional one and the modified one). The effectiveness of these statistics from the metrological point of view is examined, and the preferability of the modified kappa statistics is demonstrated via an example.     

Challenges and strategies in the preparation of large‐volume polymer‐based monolithic chromatography adsorbents

To date, the number of published reports on the large‐volume preparation of polymer‐based monolithic chromatography adsorbents is still lacking and is of great importance. Many critical factors need to be considered when manufacturing a large‐volume polymer‐based monolith for chromatographic applications. Structural integrity, validity, and repeatability are thought to be the key factors determining the usability of a large‐volume monolith in a separation process. In this review, we focus on problems and solutions pertaining to heat dissipation, pore size distribution, “wall channel” effect, and mechanical strength in monolith preparation. A template‐based method comprising sacrificial and nonsacrificial techniques is possibly the method of choice due to its precise control over the porous structure. However, additional expensive steps are usually required for the template removal. Other strategies in monolith preparation are also discussed.     

Statistical quality control for ternary ordinal quality data

The paper considers various aspects of statistical quality control by means of sample data received on a ternary ordinal scale. A new method for evaluating quality level and dispersion, free of any latent numerical scale assumptions, is proposed. The emphasis is on working with large samples, which enable the statistical analysis, estimation and control by the use of approximate analytical expressions of these measures to be considerably simplified. Two complementary studies demonstrate the usage of the proposed approach. Copyright © 2010 John Wiley & Sons, Ltd.     

Structural elucidation of V‐type nerve agents by liquid chromatography/electrospray ionization mass spectrometry

V‐nerve agents present information‐poor spectra, both in GC‐EI‐MS and LC‐ESI‐MS/MS, with dominant fragments/product ions corresponding to the amine‐containing residue. Hence, derivatives/isomers with the same amine residue exhibit similar mass spectral patterns, leading to ambiguity in the phosphonate structure. We present a simple approach for their structural elucidation based on two complementary experiments: ESI‐MS/MS of the original compound, which provides information about the amine moiety, and ESI‐MS/MS of the phosphonic acid hydrolysis products generated by N‐iodosuccinimide, which provides ions' characteristic of the phosphonate structure. This approach enables the structural elucidation of the original V‐agents with a higher degree of certainty.     

New Concepts for Designing d10‐M(L)n Catalysts: d Regime,s Regime and Intrinsic Bite‐Angle Flexibility

Our aim is to understand the electronic and steric factors that determine the activity and selectivity of transition‐metal catalysts for cross‐coupling reactions. To this end, we have used the activation strain model to quantum‐chemically analyze the activity of catalyst complexes d¹⁰‐M(L)_n toward methane C?H oxidative addition. We studied the effect of varying the metal center M along the nine d¹⁰ metal centers of Groups 9, 10, and 11 (M=Co^?, Rh^?, Ir^?, Ni, Pd, Pt, Cu⁺, Ag⁺, Au⁺), and, for completeness, included variation from uncoordinated to mono‐ to bisligated systems (n=0, 1, 2), for the ligands L=NH₃, PH₃, and CO. Three concepts emerge from our activation strain analyses: 1) bite‐angle flexibility, 2) d‐regime catalysts, and 3) s‐regime catalysts. These concepts reveal new ways of tuning a catalyst’s activity. Interestingly, the flexibility of a catalyst complex, that is, its ability to adopt a bent L‐M‐L geometry, is shown to be decisive for its activity, not the bite angle as such. Furthermore, the effect of ligands on the catalyst’s activity is totally different, sometimes even opposite, depending on the electronic regime (d or s) of the d¹⁰‐M(L)_n complex. Our findings therefore constitute new tools for a more rational design of catalysts.