The effect of phenoxy oxygen atoms on extremely high extraction ability and less separation efficiency of trivalent rare earth elements with tetraphosphonic acid derivative of calix[4]arene

A cone confomational p-t-octylcalix[4]arene with four methylenephosphonic acids at the lower rim as well as its monomeric analog have been synthesized as a new extraction reagent to investigate the extraction behavior of the nine trivalent rare earth elements: Y, La, Pr, Nd, Sm, Eu, Gd, Ho and Er. The new calix[4]arene exhibited significantly higher extraction capacity than not only the monomeric derivative and the commercial extraction reagent, 2-ethylhexyl hydrogen 2-ethylhexylphosphonate, but also the cone conformational calix[4]arene extractants employed in our previous work, composed of a tetrapropylenephosphonic acid with a longer spacer, a tetraphosphonic acid at the upper rim, and tetraacetic acid at the lower rim. A dependence on the pH was observed for the new extractant in the highly acidic region, and the extraction took place via a simple ion-exchange mechanism. Using slope analysis, the stoichiometries of tetrameric and monomeric extractants to rare earth metal ions were determined to be 2:1 and 3:1, respectively. Using the proposed extraction equations, extraction equilibrium constants and separation factors were estimated. The extremely high extraction ability and moderate separation efficiency were attributed to the chelating effect of the phosphonic acid and the phenoxy oxygen atom. The effect of the phenoxy oxygen atom on extraction ability and separation efficiency of calix[4]arene derivatives was found to be significant.     

Syntheses of Methyl 2,3-di-O-Glycyl-α-D-glucopyranoside and 4,6-di-O-Glycyl-2,3-di-O-methyl-α-D-glucopyranoside,and Removal of Aminoacyl Groups from Sugar Moieties

Abstract

To confirm the potential usefulness of amino acid residues as protecting groups for sugar hydroxyls, methyl 2,3-di-O-glycyl-α-D-glucopyranoside (5) and methyl 4,6-di-O-glycyl-2,3-di-O-methyl-α-D-gluco-pyranoside (7) were synthesized as reference compounds. Conditions were then established for the removal of these aminoacyl groups from the sugar molecules. The reference compounds were easily prepared by condensation of methyl α-D-glucopyranoside derivatives with N-protected glycine in the presence of dicyclohexyl-carbodiimide (DCC). The aminoacyl groups were removed by alkaline treatment, as were conventional acyl groups and also with ease by enzymatic hydrolysis using Pronase E. Conventional ester and ether protecting groups are not removed by such enzymatic treatment. Removal of aminoacyl group from sugar moieties on a practical scale is also described.     

Synthesis of monodispersed silica nanoparticles with high concentration by the Stöber process

Silica nanoparticles with high concentration were prepared by the sol–gel process based on the Stöber method using tetraethoxysilane as a starting material. It was found that silica sol with about 4 wt% in concentration and with a diameter of about 10 nm was obtained by controlling the reaction conditions in the Stöber process. By removing the solvent under a reduced pressure, the particle concentration was increased up to 15 wt% without aggregation.     

Interpretation of TOF-SIMS data based on information entropy of spectra

Time-of-flight secondary ion mass spectrometry (TOF-SIMS), when used for the analysis of complex material samples, typically provides data that are complicated and challenging to understand. Therefore, additional data analysis techniques, such as multivariate analysis, are often required to facilitate the interpretation of TOF-SIMS data. In this study, a new method based on the information entropy (Shannon entropy) is proposed as an indicator of the outline characteristics of an unknown sample, such as changes in the material within the sample and mixing conditions. The Shannon entropy values are calculated using the relative intensity of every secondary ion normalized to the total ion count and reflect the diversity of secondary ions in the spectrum. Mixed samples containing two organic electroluminescence materials of different ratios, multilayers of Irganox 1010, and other organic materials were employed to evaluate the utility of Shannon entropy in the analysis of TOF-SIMS data. The findings demonstrate that the Shannon entropy of a spectrum indicates differences in materials and changes in the conditions of a material in a sample without the need for peak identification or the knowledge of specific peaks corresponding to the materials in the sample.     

Selective ablation of atherosclerotic lesions with less thermal damage by controlling the pulse structure of a quantum cascade laser in the 5.7-µm wavelength range

Cholesteryl esters are the main components of atherosclerotic plaques, and they have an absorption peak at the wavelength of 5.75 µm. To realize less-invasive ablation of the atherosclerotic plaques using a quasi-continuous wave (quasi-CW) quantum cascade laser (QCL), the thermal effects on normal vessels must be reduced. In this study, we attempted to reduce the thermal effects by controlling the pulse structure. The irradiation effects on rabbit atherosclerotic aortas using macro pulse irradiation (irradiation of pulses at intervals) and conventional quasi-CW irradiation were compared. The macro pulse width and the macro pulse interval were determined based on the thermal relaxation time of atherosclerotic and normal aortas in the oscillation wavelength of the QCL. The ablation depth increased and the coagulation width decreased using macro pulse irradiation. Moreover, difference in ablation depth between the atherosclerotic and normal rabbit aortas using macro pulse irradiation was confirmed. Therefore, the QCL in the 5.7-µm wavelength range with controlling the pulse structure was effective for less-invasive laser angioplasty.     

Third-order aberration analysis of an off-axial optical system

The aberration theory applied to co-axial optical systems is extended to off-axial systems, for which third-order aberration coefficients are considered. The derived aberrations are analyzed using three-dimensional ray bundles, spot diagrams, and image charts, and classified in relation to the system symmetry. This theory is very useful for optical designers, allowing them to clarify the relationship between the structures of off-axial optical systems and the corresponding off-axial aberrations.     

Second-harmonic-generation microscope using eight-segment polarization-mode converter to observe three-dimensional molecular orientation

We developed a compact polarization-mode converter for microscopy to control three-dimensional polarization at the focus. The converter consisted of two homogeneously aligned liquid-crystal spatial light modulators with eight independently controllable electrodes (segments), and a quarter-waveplate. The converter converted a linearly polarized beam to three polarization modes: two orthogonal linear polarizations and a pseudo-radial polarization. We applied the converter to second-harmonic-generation microscopy and demonstrated the detection of three-dimensional molecular orientation.     

Blue emission from InGaN/GaN hexagonal pyramid structures

Cathodoluminescence (CL) from InGaN grown on GaN hexagonal pyramid structures has been investigated. The facet structure can be controlled by the growth temperature and reactor pressure. GaN pyramid structures surrounded with facets were grown at 1020 C at a pressure of 500 Torr by low-pressure metalorganic vapor phase epitaxy (LP-MOVPE). The indium mole fraction in the InGaN film depends on the facet structure. The thickness of the InGaN and the peak wavelength and intensity of the CL from the InGaN gradually increased from the bottom to the top of the facets.