New phosphine oxide aziridinyl phosphonates as chiral Lewis bases for the Abramov-type phosphonylation of aldehydes

A series of Lewis bases were screened for Abramov-type phosphine additions to aldehydes. A novel phosphine oxide aziridinyl phosphonate POAP-A was found to be better than the others in forming the product in 96% yield and with 42% ee. The absolute configuration of the newly synthesized POAP Lewis bases was determined by single-crystal X-ray analysis.     

Thermodynamic parameters of TI+, Ra2+, Bi3+and Ac3+ adsorption onto polyhydroxyethylmethacrylate-hydroxyapatite composite

In this research, a new composite, poly (hydroxyethylmethacrylate-hydroxyapatite) [P(HEMA-Hap)], was synthesized and its adsorptive features for natural radionuclides (TI⁺, Ra²⁺, Bi³⁺and Ac³⁺ in a leaching solution) were investigated at differing initial pH, concentration and temperature ranges. The natural radionuclides were counted by gamma spectrometer using a type NAI (Tl) detector. The adsorption data obtained were well represented by Langmuir and Freundlich type isotherms. The magnitude of determined monolayer adsorption capacities (X _L) for the adsorbed radionuclides were TI⁺ = Ac³⁺ > Ra²⁺ = Bi³⁺. These results demonstrated that P(HEMA-Hap) had high affinity to the natural radionuclide. The thermodynamic parameters indicated that the adsorption mechanisms were spontaneous (ΔG < 0) in terms of adsorption free enthalpy, and changes in the enthalpy and entropy values showed that the overall adsorption process was endothermic (ΔH > 0), thus increasing entropy (ΔS > 0).     

HPLC Separation of Different Groups of Small Polar Compounds on a Novel Amide-Embedded Stationary Phase

Retention behaviors of an amide-embedded silica base stationary phase, which was recently developed by our group, were studied by using six different groups of small polar compounds including phenolic compounds, substituted anilines, chlorinated herbicides, Sudan dyes and some nucleotides and nucleosides in HPLC. The chromatographic behaviors of the prepared stationary phase for these analytes were compared with those of a commercially available reversed-phase column ACE C18 under same conditions. Among the six groups of analytes studied, the amide-silica stationary phase showed enhanced selectivity towards phenolic compounds, substituted anilines, Sudan dyes and herbicides under reversed-phase conditions and satisfactory selectivity towards nucleosides and nucleotides which could not be separated with ACE C18 column under HILIC conditions. Experimental data provided some evidence that functional groups on the stationary phases might have certain degrees of influence on selectivity possibly through secondary interactions with the model compounds. The retentions of the moderately polar compounds such as phenolic acids, anilines and herbicides on the stationary phase are higher than highly polar compounds such as nucleotides and nucleosides due to both the hydrophobic and hydrophilic interactions between the stationary phase and analytes. The quantitative determination of Sudan dyes (I, II, III, and IV) in red chilli peppers was performed. Many red chilli peppers were screened and three of them contained Sudans dyes.     

Characterization of bidentate phosphoryl compounds on soil particulates using SIMS

The presence of organic compounds as surface contaminants on particles can provide valuable data about the particles environment, but identification can be analytically challenging. This is true particularly for compounds that have the potential for strong surface binding, such as compounds capable of multidentate attachment. Direct analysis using time‐of‐flight secondary ion mass spectrometry was evaluated for characterization of soil particles contaminated with low concentrations of two bidentate organophosphoryl compounds, diphenyl‐N,N‐di‐n‐butylcarbamoylmethylphosphine oxide and tetraphenylmethylene diphosphine dioxide. Molecular ions were formed by cationization with H⁺ and alkali elements Na⁺ and K⁺ that are indigenous to the particle surface chemistry. Spectra generated from a contaminated calcareous soil were dominated by K⁺‐containing ions, whereas spectra from a sandy loam had more abundant Na⁺‐species. Cation‐bound dimers were also formed which favored incorporation of K⁺, and a unique aluminosilicate‐phosphoryl conjugate cation was also formed when the diphosphoryl ligand was present on the surface. The phosphoryl ligands also underwent fragmentation reactions, the course of which varied depending on the cation that was bound. Minimum detectable surface concentrations were evaluated and were in the 0.04–0.2 monolayer range, depending on the compound and soil particle matrix they was bound to. The ion signature was detected on soil particle surfaces for time periods exceeding six months, suggesting that the characterization approach could be used for environmental exposure history at times well beyond initial exposure. Copyright © 2009 John Wiley & Sons, Ltd.     

An electron paramagnetic resonance and density-functional theory study on the methyl isotropic hyperfine coupling constants in gamma-irradiated 2,6-di-tert-butyl-4-methylphenol

Single crystal of gammairradiated 2,6-di-tert-butyl-4-methylphenol (BHT) was investigated using an electron paramagnetic resonance (EPR) technique at different orientations in the magnetic field at room temperatures. Taking into consideration the chemical structure and the experimental spectra of the irradiated single crystal of BHT, we assumed that one phenoxyltype paramagnetic species was produced having an unpaired electron localized at the methyl fragment side of the phenyl ring. Depending on this assumption, one possible radical was modeled using the B3LYP/6-311+G(d) level of density-functional theory. EPR parameters were calculated for these modeled radical using the B3LYP/TZVP and B3LYP/EPR-III level. The averaged value of isotropic hydrogen hyperfine coupling constants of rotating methyl functional group of phenoxyl radical is calculated for the first time. Theoretically calculated values of the modeled radical are in reasonably good agreement with the experimental data determined from the spectra (differences in averaged coupling constant values smaller than 5%, and differences in isotropic g values fall into 1 ppt).     

Preparation and characterization of radiolabeled magnetic nanoparticles as an imaging agent

The degradation of crystal violet in aqueous solution was investigated using kaolin-supported zero-valent iron nanoparticles (K-nZVI). It was found that K-nZVI with a ratio of kaolin:zero-valent iron nanoparticles (nZVI) at 1:1 was most effective in removing crystal violet. Batch experiments show that more than 97.29?% crystal violet was degraded using K-nZVI, while only 24.36?% was removed using nZVI after reacting for 7?min, where the solution contained 100?mg?L^?1 crystal violet at pH 6.5. This is due to a decrease in aggregation of Fe⁰ nanoparticles and enhanced their reactivity in the presence of kaolin, which was confirmed by the characterization using scanning electron microscopy. X-ray diffraction shows the formation of iron oxide and hydroxide, while UV?CVis spectral shows that the absorption peak of crystal violet was reduced, as well as Fourier transform infrared shows that new bands were formed after K-nZVI reacting with crystal violet. These suggest that degradation of crystal violet by K-nZVI include the oxidation of iron, the adsorption of crystal violet onto the K-nZVI, the transformation of crystal violet to leuko-crystal violet, and finally the cleavage of C=C bond.     

Interferometric measurements of the anomalous thermal expansion in single crystal dysprosium and 60% Gadolinium-Yttrium

An optical interferometer technique employed in the measurement of the c-axis thermal expansion in single crystal Dy confirms previous strain gauge observations that the expansion and Néel temperature are dependent on the internal strain in the crystal. The technique reveals that similar effects can be observed in single crystal 60% Gd-y although this material is less susceptible than dysprosium to internal strain produced by thermal cycling. The consequences of the deviations in c-axis expansion are discussed.     

HEPES-stabilized encapsulation of Salmonella typhimurium

Most bacteria, planktonic and sessile, are encapsulated inside loosely bound extracellular polymeric substance (EPS) in their physiological environment. Imaging a bacterium with its capsule requires lengthy sample preparation to enhance the capsular contrast. In this study, Salmonella typhimurium was investigated using atomic force microscopy for a practical means of imaging an encapsulated bacterium in air. The investigation further aimed to determine the relation between the buffers used for preparing the bacterium and the preservation of the capsular material surrounding it. It was observed that rinsing bacteria with HEPES buffer could stabilize and promote capsule formation, while rinsing with PBS, Tris, or glycine removes most of the capsular EPS. For bacteria rinsed with HEPES and air-dried, the height images showed only the contour of the capsular material, while the phase and amplitude images presented the detailed structures of the bacterial surface, including the flagella encapsulated inside the capsular EPS. The encapsulation was attributed to the cross-linking of the acidic exopolysaccharides mediated by the piperazine moiety of HEPES through electrostatic attraction. This explanation is supported by encapsulated bacteria observed for samples rinsed with N,N'-bis(2-hydroxyethyl)-piperazine solution and by the presence of entrapped HEPES within the dry capsular EPS suggested by micro-Raman spectroscopy.     

Photoinduced step-growth polymerization of thieno[3,4-b] thiophene derivatives. The substitution effect on the reactivity and electrochemical properties

We herein report photoinduced step-growth polymerization of highly conjugated 2,5-dithiophenyl (thieno[3,4-b] thiophene) (TTs) derivatives possessing 4-cyanophenyl or 4-methoxyphenyl or 3-(4-fluorophenyl) groups substituted at the terminal position. Upon irradiation at 350 nm, the excited state of these molecules forms exciplex with diphenyliodonium hexafluorophosphate (DPI) that undergoes electron transfer reaction forming radical cations. Successive proton release and radical coupling reactions yield corresponding oligothienothiophenes with overall yields varying between 19–74%. Structural and molecular weight characteristics of the oligomers thus formed were investigated by Ultraviolet, fluorescence, NMR (Nuclear Magnetic Resonance) and infrared (IR) spectroscopic methods, and GPC (Gel Permeation Chromatography), respectively. The effect of substitution and dithiophene side groups on the reactivity of the monomer and band gap of the oligomers formed was evaluated by using cyclic voltammetry.     

Radiometric mapping and radiation dose assessments in sediments from Şavşat Black Lake,Turkey

Journal of Radioanalytical and Nuclear Chemistry - In this study, natural and artificial radioactivity concentrations in sediment samples taken from ?av?at Black Lake located on the...