Some Aspects of the Chemistry of Samarium (II) Compounds

Although the normal oxidation state of the rare earth elements is the tripositive one, several of them are capable of exhibiting either a lower or a higher valence of variable degrees of stability. Of particular interest in this investigation was the divalent state exhibited by samarium. It is well known that half-filled electronic shells tend to be rather stable. Divalent europium with electronic configuration of Xe 4f7* forms quite stable compounds which are slowly oxidized by water. Another stable rare earth divalent ion is Yb++ where the 4f shell is complete, (Xe 4f14), divalent samarium ion, on the other hand, only approaches a half filled shell (Xe 4f6 ) and is consequently extremely susceptible to oxidation. The first known samarium (II) compound was the chloride prepared by Matignon in 1906 (1). Later investigators prepared the bromide (2) and the iodide (3). All of these compounds were obtained by hydrogen or ammonia reduction of the corresponding trivalent halides at elevated temperatures. The iodide can likewise be prepared by the thermal decomposition of the SmI3 (3). Several of the divalent samarium compounds have been prepared by metathetical reactions in aqueous solutions; the sulfate, the chromate and the phosphate by Jantsch and Skalla (3) and the fluoride, the citrate and the carbonate by Clifford and Beachell (4). Of all these compounds only the sulfate could be isolated and analyzed. Several investigators have reported a green colored samarium (II) compound (4, 5) which was, presumably, either a carbonate or a hydroxide. The unusual color is rather interesting since all other compounds of divalent samarium are red

Geometric discrete analogues of tangent bundles and constrained Lagrangian systems

Discretizing variational principles, as opposed to discretizing differential equations, leads to discrete-time analogues of mechanics, and, systematically, to geometric numerical integrators. The phase space of such variational discretizations is often the set of configuration pairs, analogously corresponding to initial and terminal points of a tangent vectors. We develop alternative discrete analogues of tangent bundles, by extending tangent vectors to finite curve segments, one curve segment for each tangent vector. Towards flexible, high order numerical integrators, we use these discrete tangent bundles as phase spaces for discretizations of the variational principles of Lagrangian systems, up to the generality of nonholonomic mechanical systems with nonlinear constraints. We obtain a self-contained and transparent development, where regularity, equations of motion, symmetry and momentum, and structure preservation, all have natural expressions.Comment: Typos corrected. New abstract. Diagrams added. Some additional information and a conclusions section adde

Dual Action Additives for Jet A-1: Fuel Dehydrating Icing Inhibitors

© 2016 American Chemical Society. A novel approach for protecting jet fuel against the effects of water contamination based upon Fuel Dehydrating Icing Inhibitors (FDII) is presented. This dual-action strategy is predicated on the addition of a fuel-soluble water scavenger that undergoes a kinetically fast hydrolysis reaction with free water to produce a hydrophilic ice inhibitor, thereby further militating against the effects of water crystallization. Criteria for an optimum FDII were identified and then used to screen a range of potential water-scavenging agents, which led to a closer examination of systems based upon exo/endo-cyclic ketals and both endo- and exo-cyclic ortho esters. The ice inhibition properties of the subsequent products of the hydrolysis reaction in Jet A-1 were screened by differential scanning calorimetry. The hydrolysis products of 2-methoxy-2-methyl-1,3-dioxolane demonstrate similar ice inhibition performance to DiEGME over a range of blend levels. The calorific values for the products of hydrolysis were also investigated, and it is clear that there would be a significant fuel saving on use of the additive over current fuel system icing inhibitors. Finally, three promising candidates, 2-methoxy-2-methyl-1,3-dioxolane, 2-methoxy-2-methyl-1,3-dioxane, and 2-methoxy-2,4,5-trimethyl-1,3-dioxolane, were shown to effectively dehydrate Jet A-1 at room temperature over a 2 h period

Review of Student-Built Spectroscopy Instrumentation Projects

Copyright © 2020 American Chemical Society and Division of Chemical Education, Inc. One challenge of teaching chemical analysis is the proliferation of sophisticated, but often impenetrable, instrumentation in the modern laboratory. Complex instruments, and the software that runs them, distance students from the physical and chemical processes that generate the analytical signal. A solution to this challenge is the introduction of a student-driven instrument-building project. Visible absorbance spectroscopy is well-suited to such a project due to its relative simplicity and the ubiquity of absorbance measurements. This Article reviews simple instructor- A nd student-built instruments for spectroscopy, providing an overview of common designs, components, and applications. This comprehensive summary includes options that are suitable for in-person or remote learning with K-12 students and undergraduates in general chemistry, analytical chemistry, instrumental analysis, and electronics courses

Host investment into symbiosis varies among genotypes of the legume Acmispon strigosus, but host sanctions are uniform.

Efficient host control predicts the extirpation of ineffective symbionts, but they are nonetheless widespread in nature. We tested three hypotheses for the maintenance of symbiotic variation in rhizobia that associate with a native legume: partner mismatch between host and symbiont, such that symbiont effectiveness varies with host genotype; resource satiation, whereby extrinsic sources of nutrients relax host control; and variation in host control among host genotypes. We inoculated Acmispon strigosus from six populations with three Bradyrhizobium strains that vary in symbiotic effectiveness on sympatric hosts. We measured proxies of host and symbiont fitness in single- and co-inoculations under fertilization treatments of zero added nitrogen (N) and near-growth-saturating N. We examined two components of host control: 'host investment' into nodule size during single- and co-inoculations, and 'host sanctions' against less effective strains during co-inoculations. The Bradyrhizobium strains displayed conserved growth effects on hosts, and host control did not decline under experimental fertilization. Host sanctions were robust in all hosts, but host lines from different populations varied significantly in measures of host investment in both single- and co-inoculation experiments. Variation in host investment could promote variation in symbiotic effectiveness and prevent the extinction of ineffective Bradyrhizobium from natural populations

Recurrent mutualism breakdown events in a legume rhizobia metapopulation.

Bacterial mutualists generate major fitness benefits for eukaryotes, reshaping the host phenotype and its interactions with the environment. Yet, microbial mutualist populations are predicted to generate mutants that defect from providing costly services to hosts while maintaining the capacity to exploit host resources. Here, we examined the mutualist service of symbiotic nitrogen fixation in a metapopulation of root-nodulating Bradyrhizobium spp. that associate with the native legume Acmispon strigosus. We quantified mutualism traits of 85 Bradyrhizobium isolates gathered from a 700 km transect in California spanning 10 sampled A. strigosus populations. We clonally inoculated each Bradyrhizobium isolate onto A. strigosus hosts and quantified nodulation capacity and net effects of infection, including host growth and isotopic nitrogen concentration. Six Bradyrhizobium isolates from five populations were categorized as ineffective because they formed nodules but did not enhance host growth via nitrogen fixation. Six additional isolates from three populations failed to form root nodules. Phylogenetic reconstruction inferred two types of mutualism breakdown, including three to four independent losses of effectiveness and five losses of nodulation capacity on A. strigosus. The evolutionary and genomic drivers of these mutualism breakdown events remain poorly understood

Integrable discretizations of some cases of the rigid body dynamics

A heavy top with a fixed point and a rigid body in an ideal fluid are important examples of Hamiltonian systems on a dual to the semidirect product Lie algebra $e(n)=so(n)\ltimes\mathbb R^n$. We give a Lagrangian derivation of the corresponding equations of motion, and introduce discrete time analogs of two integrable cases of these systems: the Lagrange top and the Clebsch case, respectively. The construction of discretizations is based on the discrete time Lagrangian mechanics on Lie groups, accompanied by the discrete time Lagrangian reduction. The resulting explicit maps on $e^*(n)$ are Poisson with respect to the Lie--Poisson bracket, and are also completely integrable. Lax representations of these maps are also found.Comment: arXiv version is already officia

Molecular biology of histidine decarboxylase and prostaglandin receptors

Histamine and prostaglandins (PGs) play a variety of physiological roles as autacoids, which function in the vicinity of their sources and maintain local homeostasis in the body. They stimulate target cells by acting on their specific receptors, which are coupled to trimeric G proteins. For the precise understanding of the physiological roles of histamine and PGs, it is necessary to clarify the molecular mechanisms involved in their synthesis as well as their receptor-mediated responses. We cloned the cDNAs for mouse l-histidine decarboxylase (HDC) and 6 mouse prostanoid receptors (4 PGE2 receptors, PGF receptor, and PGI receptor). We then characterized the expression patterns and functions of these genes. Furthermore, we established gene-targeted mouse strains for HDC and PG receptors to explore the novel pathophysiological roles of histamine and PGs. We have here summarized our research, which should contribute to progress in the molecular biology of HDC and PG receptors

Effects of crystallization and dopant concentration on the emission behavior of TiO2:Eu nanophosphors

Uniform, spherical-shaped TiO2:Eu nanoparticles with different doping concentrations have been synthesized through controlled hydrolysis of titanium tetrabutoxide under appropriate pH and temperature in the presence of EuCl3·6H2O. Through air annealing at 500°C for 2 h, the amorphous, as-grown nanoparticles could be converted to a pure anatase phase. The morphology, structural, and optical properties of the annealed nanostructures were studied using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy [EDS], and UV-Visible diffuse reflectance spectroscopy techniques. Optoelectronic behaviors of the nanostructures were studied using micro-Raman and photoluminescence [PL] spectroscopies at room temperature. EDS results confirmed a systematic increase of Eu content in the as-prepared samples with the increase of nominal europium content in the reaction solution. With the increasing dopant concentration, crystallinity and crystallite size of the titania particles decreased gradually. Incorporation of europium in the titania particles induced a structural deformation and a blueshift of their absorption edge. While the room-temperature PL emission of the as-grown samples is dominated by the 5D0 - 7Fj transition of Eu+3 ions, the emission intensity reduced drastically after thermal annealing due to outwards segregation of dopant ions

Determination of the melting temperature, heat of fusion, and purity analysis of different samples of zidovudine (AZT) using DSC

The determination of chemical purity, melting range, and variation of enthalpy in the process of characterizing medicines is one of the principal requirements evaluated in quality control of the pharmaceutical industry. In this study, the method of purity determination using DSC was outlined, as well as the application of this technique for the evaluation of commercial samples of zidovudine (AZT) (raw material) supplied by different laboratories. To this end, samples from six different laboratories (A, B, C, D, E, and F) and the standard reference (R) from the United States Pharmacopeia (USP) were analyzed. The DSC curves were obtained in the temperature range of 25 to 200 ºC under the dynamic atmosphere of N2 (50 mL min-1), heating rate of β=2 ºC min-1, using an Al capsule containing approximately 2 mg of sample material. The results demonstrated that the standard reference presented a proportion of 99.83% whereas the AZT samples presented a variation ranging from 97.59 to 99.54%. In addition, the standard reference was found to present a temperature of onset of melting point of 122.80 °C. Regarding the samples of active agents provided by the different laboratories, a variation ranging from 118.70 to 122.87 °C was measured. In terms of ΔHm, the samples presented an average value of 31.12 kJ mol-1._________________________________________________________________________________________ RESUMO: A determinação da pureza química, a faixa de fusão e a variação de entalpia envolvida no processo de caracterização de fármacos é um dos principais requisitos avaliados no controle de qualidade em indústrias farmacêuticas. Neste trabalho é feita uma breve abordagem sobre o método de determinação de pureza utilizando DSC, assim como a aplicação desta técnica para avaliação de amostras comerciais de zidovudina (AZT) (matéria-prima) fornecida por diferentes laboratórios. Para tal, foram analisadas amostras de seis diferentes laboratórios (A,B,C,D,E e F) e a substância química de referência (R) da United States Pharmacopeia (USP). As curvas DSC foram obtidas na faixa de temperatura entre 25 a 200 ºC, sob atmosfera dinâmica de N2 (50 mL min-1), β=2 ºC min-1, utilizando cápsula de Al contendo aproximadamente 2 mg de amostra. De acordo com os resultados, pode-se observar que a substância química de referência apresentou teor igual a 99,83% e que as amostras de AZT apresentaram uma faixa de variação entre 97,59 e 99,54%. Pode-se verificar, ainda, que a substância química de referência apresentou uma temperatura onset de fusão igual a 122,80 °C. Para as amostras dos princípios ativos fornecidos pelos diferentes laboratórios, pode-se verificar uma faixa de variação entre 118,70 e 122,87 °C. No que se refere ao ΔHm, as amostras apresentaram valor médio de 31,12 kJ.mol-1