Chiral Etch Pits on Sodium Chlorate Crystals

Microtopography of {100}, {110}, {111}, and {210} surfaces of sodium chlorate crystals etched in various solvents has been studied by optical microscopy. It has been established that etch pits formed on left- and right-handed crystals are chiral, and directions of dissolution steps reveal bond chains of the structure.     

Nucleophilic Substitution at Heteroatoms—Identity Substitution Reactions at Phosphorus and Sulfur Centers: Do They Proceed in a Concerted (SN2) or Stepwise (A–E) Way?

The mechanisms of three selected identity substitution reactions at phosphorus and sulfur occurring with stereospecific inversion have been investigated using density functional theory (DFT). The first identity reaction between methoxyl anion and methyl ethylphenylphosphinate 1 reported in 1963 has been shown to proceed in a stepwise fashion according to the addition–elimination (A–E) mechanism involving formation of a pentacoordinate phosphorus intermediate (TBI-1). In contrast, the results of DFT studies of the identity chloride exchange reaction in (ethoxy)ethylphosphonochloridothionate 3 in acetone solution provided evidence that it proceeds synchronously according to the classical Ingold’s S_N2-P mechanism. DFT calculations of the methoxyl–methoxy exchange reaction at sulfur in methyl p-toluenesulfinate 4 catalyzed by trifluoroacetic acid in methanol revealed that it proceeds stepwise (A–E mechanism), involving the formation of the high-coordinate sulfurane intermediate. In both identity transesterification reactions, 1 and 4, the transiently formed trigonal bipyramidal intermediates with the two methoxyl groups occupying apical positions (TBI-1 and TBI-4) have higher free energy barriers for the Berry-type pseudorotation than those for direct decomposition to starting phosphinate and sulfinate ensuring stereospecific inversion of configuration at the phosphinyl and sulfinyl centers. Thus, the DFT method proved its usefulness in the distinction between both mechanisms that are often indistinguishable by kinetic measurements.     

On the Critical Growth Velocities for the Presence of Faces on Growing Crystals

Faces of three-dimensional crystals have been divided into edge and corner ones to describe the phenomenon of their disappearance and appearance during the crystal growth. The expression for the critical growth velocity governing the presence of corner faces has been derived and verified and the validity of the previous relationship (SZURGOT , PRYWER ) for the edge faces confirmed. Three nearest neighbours control the presence of corner faces and two neighbours decide on the edge faces.     

On the Formation of Thick Sector Boundaries by Appearance and Disappearance of Faces of Crystals

Wide sector boundaries revealed in KBC crystals by chemical etching have been observed and analysed. It was established that the boundaries represent sectors of small faces appearing and vanishing in the habit during crystal growth. This nature of thick boundaries has been confirmed by the analysis of values of relative growth velocities of faces with respect to the critical velocities governing the presence of faces on growing crystals.     

Biofortification—A Frontier Novel Approach to Enrich Micronutrients in Field Crops to Encounter the Nutritional Security

Globally, many developing countries are facing silent epidemics of nutritional deficiencies in human beings and animals. The lack of diversity in diet, i.e., cereal-based crops deficient in mineral nutrients is an additional threat to nutritional quality. The present review accounts for the significance of biofortification as a process to enhance the productivity of crops and also an agricultural solution to address the issues of nutritional security. In this endeavor, different innovative and specific biofortification approaches have been discussed for nutrient enrichment of field crops including cereals, pulses, oilseeds and fodder crops. The agronomic approach increases the micronutrient density in crops with soil and foliar application of fertilizers including amendments. The biofortification through conventional breeding approach includes the selection of efficient genotypes, practicing crossing of plants with desirable nutritional traits without sacrificing agricultural and economic productivity. However, the transgenic/biotechnological approach involves the synthesis of transgenes for micronutrient re-translocation between tissues to enhance their bioavailability. Soil microorganisms enhance nutrient content in the rhizosphere through diverse mechanisms such as synthesis, mobilization, transformations and siderophore production which accumulate more minerals in plants. Different sources of micronutrients viz. mineral solutions, chelates and nanoparticles play a pivotal role in the process of biofortification as it regulates the absorption rates and mechanisms in plants. Apart from the quality parameters, biofortification also improved the crop yield to alleviate hidden hunger thus proving to be a sustainable and cost-effective approach. Thus, this review article conveys a message for researchers about the adequate potential of biofortification to increase crop productivity and nourish the crop with additional nutrient content to provide food security and nutritional quality to humans and livestock.     

The development of spherulite morphology in polymers

Morphology of polyethylene spherulites has been investigated by the low-dose technique using transmission electron microscopy (TEM) in a scanning mode for dark field and microdiffraction. Specimens were prepared by solvent casting and subsequent recrystallization at different temperatures. The dark-field studies provide spatial information on the lamellar morphology. Two major types of spherulite morphology have been observed: At high temperatures (low crystallization rate) the dark fields show a preferred orientation of the lamellae along the 020 axis. At low temperatures the preferred orientation is 110. The microdiffraction patterns confirm the dark-field results and also show that for intermediate temperatures, regular alteration of regions with 020 and 110 growth planes is responsible for the ringed spherulite appearance. The twisted lamellae model cannot be excluded, but it is shown that it is not responsible for the regular changes in contrast. A model of dendritic growth of spherulite lamellae is used in which the plane of crystal growth is temperature dependent and, for intermediate temperatures, results in regular fluctuation in the mode of crystal growth, branching, and ringed spherulites appearance.     

Highly oriented crystalline Er:YAG and Er:YAP layers prepared by PLD and annealing

High quality, thick, highly oriented crystalline thin films of Yttrium Aluminum Garnet (Y₃Al₅O₁₂) and Yttrium Aluminum Perovskite (YAlO₃) doped with Erbium were prepared by pulsed laser deposition. Samples were created in vacuum or oxygen environment. Depositions were arranged at room temperature, or at high substrate temperatures ranging from 800 to 1100 °C. Amorphous layers were annealed by laser, or in oven (argon flow, temperatures in range from 1200 to 1400 °C). Fused silica and sapphire (0 0 0 1) were used as substrates. Properties of films were characterized by X-ray diffraction, atomic force microscopy, and by photoluminescence measurement. Size of crystalline grains was in the range 116-773 nm. Thickness of layers was up to 17 μm.     

A semi-empirical approach to determine gamma activities in environmental cylindrical samples

A semi-empirical method to determine radionuclide concentrations in large environmental samples without the use of reference material and avoiding the typical complexity of Monte-Carlo codes is proposed. The calculation of full-energy peak efficiencies was carried out from a relative efficiency curve (obtained from the gamma spectra data), and the geometric (simulated by Monte-Carlo), absorption, sample and intrinsic efficiencies for energies between 130 and 3000 keV. The absorption and sample efficiencies were determined from the mass absorption coefficients, whereas the intrinsic efficiency was approximated by an empirical function. The deviations between calculated and experimental efficiencies for a reference material in most cases are less than 10%. Radionuclide activities in marine sediment samples calculated by the proposed method and by the experimental comparative method were not significantly different. This new method can be used for routine environmental monitoring when uncertainties up to 10% are acceptable.     

Composition operators from large weighted Hardy spaces into the Dirichlet space

Given a large weighted Hardy space we show there exists a composition operatorC with that maps from that space into the unweighted Dirichlet space and lies in every Schatten p-class for 0<p<. This is in contrast to the situation in which the image space is a smaller weighted Dirichlet space. It is known that in that case it is not possible to find such a composition operator that is bounded.This research was supported in part by a summer stipend from Bellarmine College.