Improvement in flow-sheet of extraction chromatography for trivalent minor actinides recovery

Journal of Radioanalytical and Nuclear Chemistry - Extraction chromatography flow-sheet employing octyl(phenyl)-N,N-diisobutylcarbonoylmethylphosphine oxide and bis(2-ethylhexyl) hydrogen phosphate...     

Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis

The direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity.     

General Formation of Macro-/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits

Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.     

Extending the possibility of an N-Troc-protected sialic acid donor toward variant sialo-glycoside synthesis

The potential of an N-Troc-protected sialic acid donor, equipped with phenylsulfenyl functionality as a leaving group, has been explored. As a result, the entitled donor was proven to be highly reactive and to have broad applicability toward the synthesis of variant sialo-glycans, which have N-glycolyl, de-N-acetyl, 1,5-lactam and 8-O-sulfo sialic acid analogs.     

Phase rotation scheme of laser-produced ions for reduction of the energy spread

In order to widely spread out particle beams utilized in cancer therapy, laser-produced ions are developed as the injection beam for an ion synchrotron dedicated for cancer therapy. Such a laser ion source is expected to contribute largely to the realization of compactness of the size and low cost of the cancer therapy accelerator. The energy spectrum of the laser-produced ions, however, has no peak, but their intensities decrease exponentially according to the increase of the energy. For the purpose of modifying such a situation, we have proposed a scheme to rotate the beam in the longitudinal phase space with the use of the RF electric field, which is phase-adjusted with the pulse laser. We aim for a reduction of the energy spread of ± 5% selected by an energy analyzer and slits to ±1% by such phase rotation. For this purpose, a quarter wavelength resonator with two gaps with the same resonant frequency as the source laser has already been fabricated, together with its RF power source. The above phase rotation system and its recent experimental realization are presented.     

Anisotropic giant magnetoresistance originating from the π-d interaction in a molecule

We synthesized TPP[Fe^III(Pc)(CN)₂]₂, PTMA_x[Fe^III(Pc)(CN)₂]·y(MeCN), and PXX [Fe^III(Pc)(CN)₂], a new series of charge-transfer salts containing the axially-substituted phthalocyanine (Pc), [Fe^III(Pc)(CN)₂]⁻. In this molecular unit, the π conduction electron derived from the Pc-ring coexists with the d electron which is a potential source of a local magnetic moment. Therefore various phenomena associated with the interplay between local magnetic moments and conduction electrons are expected. We observed the giant negative magnetoresistance (GNMR) in all the three salts. The GNMR is highly anisotropic for the magnetic-field direction, and reflects the g-tensor anisotropy of the local magnetic moment in the [Fe^III(Pc)(CN)₂]⁻ unit. This indicates that the GNMR in these salts originates from the strong π-d interaction in the [Fe^III(Pc)(CN)₂]⁻ unit.     

(Triisopropylsilyl)acetaldehyde acetal as a novel protective group for 1,2-diols

(Triisopropylsilyl)acetaldehyde dimethyl acetal (TIPS-ADMA) was synthesized from chlorotriisopropylsilane in three steps. Cyclic and acyclic 1,2-diols can be transformed to (triisopropylsilyl)ethylidene acetals (TIPS-AA). Removal of the acetal by LiBF₄ regenerates the starting diol in excellent yield even in the presence of an acetonide of 1,2-diol. The TIPS-AA group can survive under the deprotection conditions of the acetonide in acetic acid at 80 °C. Selective protection of 2,3- and 4,6-diols for O-methyl d-mannoside with TIPS-ADMA and selective deprotection of the acetals have been achieved.