A versatile route to silylsubstituted ketones by rhodium catalyzed isomerization of silylated allyl alcohols

The rhodium catalyzed isomerization of α-, β-, and γ-silylated allyl alcohols has been successfully applied to the selective synthesis of acylsilane, α-silyl ketones, and β-silyl ketones, respectively.     

Preparation of Na+-selective electrodes by ion-implantation of lithium and silicon into single-crystal alumina wafer and its application to the production of ISFET

Summary Sodium ion-selective electrodes (Na⁺-ISE) were prepared by implanting Si⁺ and Li⁺ into alumina wafers and their characteristics were investigated. The alumina wafer had a thickness of 100 m and a diameter of 1.40 cm. The ionselective membrane was produced by ion-implanting of Li⁺ and Si⁺ on both sides of a single-crystal alumina wafer. The total doses of Li⁺ and Si⁺ were controlled to be the same, viz. 10¹³–10¹⁵ ions/cm². The ion-implanted alumina wafer with 10¹⁴ or 4×10¹⁴ ions/cm² of Li⁺ and Si⁺ showed better characteristics than the others.The response curves of the 10¹⁴ ions/cm² implanted alumina wafer had a slope of 42 mV/pNa in a concentration range from 1–10^–4mol/l. The full response achieved after about 1 min was reproducible. The proposed idea of producing Na⁺-ISE by ion-implantation technique was applied to functuate the gate surface of the field effect transitor to sodium ion. The sodium ion-sensitive FET (Na⁺-ISFET) prepared by implanting Li⁺ and Al⁺ at a dose of 5×10¹⁴ ions/cm² showed a slope of 30 mV/pNa in a concentration range from 1–10^–4mol/l.

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Herstellung Na⁺-ionenselektiver Elektroden durch Einbau von Lithium und Silicium in Einkristall-Alumniumoxidblättchen und Anwendung zur Erzeugung von ISFET

Zusammenfassung Na⁺-selektive Elektroden wurden durch Einbau von Si⁺ und Li⁺ in Aluminiumoxidblättchen hergestellt und ihre Charakteristiken untersucht. Die Blättchen hatten eine Dicke von 100 m und einen Durchmesser von 1,40 cm. Ebenso wurde die Membran für einen ISFET hergestellt. Die Gesamtmenge von Li⁺ und Si⁺ wurde auf 10¹³–10¹⁵ Ionen/cm² eingestellt, wobei sich bei 10¹⁴ oder 4×10¹⁴ Ionen/cm² die beste Charakteristik ergab.Die Responsekurven der mit 10¹⁴ Ionen/cm² versehenen Aluminiumoxidplättchen hatten eine Neigung von 42 mV/pNa in einem Konzentrationsbereich von 1–10^–4mol/l. Der nach 1 min erhaltene volle Response war reproduzierbar. Die vorgeschlagene Technik wurde zur Einstellung der Gate-Oberfläche des Feldeffekt-Transistors auf Natriumion benutzt. Der Na⁺-sensitive FET (Na⁺-ISFET), der durch Einbau von Li⁺ und Al⁺ mit 5×10¹⁴ Ionen/cm² hergestellt wurde, zeigte eine Neigung der Signalkurve von 30 mV/pNa in einem Bereich von 1–10^–4mol/l.

     

Stereocontrolled synthesis of α,β-unsaturated carboxylic esters from O-methyl-C,O-bis(trimethylsilyl)ketene acetal and aliphatic aldehydes

(R*,S*) Selective aldol type reaction of O-methyl-C,O-bis(trimethylsilyl)ketene acetal ($\text{1}$) with aldehydes and stereoselective formation of α,β-unsaturated carboxylic esters are attained by the combination of Z-$\text{1}$ and Lewis acids.     

Effect of temporal resolution on the estimation of left ventricular function by cardiac MR imaging

The aim of this study was to investigate the effect of temporal resolution on the estimation of left ventricular (LV) function by cardiac magnetic resonance (MR) imaging using a steady-state free precession (SSFP) sequence. Left ventricular function was assessed by cine MR imaging using a segmented SSFP sequence in 10 healthy volunteers. Views per segment (VPS) were set at 8 and 20, resulting in high and low true temporal resolution, respectively. Irrespective of VPS, images were reconstructed at 40 cardiac phases, providing high apparent temporal resolution. Data were analyzed using 40, 20 and 10 phases to simulate different apparent temporal resolutions. Increasing the cardiac phases used for analysis slightly decreased mean end-systolic volume (ESV) and slightly increased mean ejection fraction (EF). No substantial difference in estimates of end-diastolic volume (EDV) was found between VPSs of 8 and 20. Imaging with a VPS of 20 yielded a larger ESV and smaller EF than imaging with a VPS of 8 when 40 phases were used. In conclusion, low true temporal resolution causes overestimation of ESV and underestimation of EF. Improvement of apparent temporal resolution mildly reduces but does not eliminate the errors caused by low true temporal resolution.     

High Refractive-Index Microspheres as Optical Cavity Structure

Microspheres of refractive index of n_D > 2.0 have been investigated. The organic-inorganic hybrid microspheres of n_D = 1.72 were prepared by the vibrating orifice technique using titanium-tetra-n-butoxide (TTBu) and diphenyldimethoxysilane (DPhDMS). For lasing demonstration, Eu³⁺-doped microspheres were prepared using europium (III) thenoyltrifluoroacetonate [Eu(TTFA)₃] as the dopant. The particles have good spherical shape, smooth surface and high optical transparency. The diameters of the particles could be controlled to within 0.1 m. Subsequent heating of the microspheres at 550°C under oxygen atmosphere resulted in an increase in the refractive index up to n_D = 2.6 with retention of the spherical shape. Resonant emission was confirmed from Eu^{3 +}-doped microspheres after heating at 400–550°C, by pumping with the 514.5 nm line of a CW- Ar⁺laser.     

O-selectivity and utility of phosphorylation mediated by phosphite triester intermediates in the N-unprotected phosphoramidite method

Previously, O-selective phosphorylation on polymer supports in the N-unprotected phosphoramidite method could not be carried out because the amino groups of dA and dC have high reactivity toward tervalent phosphorus(III)-type phosphitylating reagents. In this paper, we developed a new coupling strategy named the "activated phosphite method" in which the phosphitylation is mediated by phosphite triester intermediates 1. Application of 1-hydroxybenzotriazole as the promoter to the solid-phase synthesis resulted in excellent O-selectivity of more than 99.7%. This O-selectivity was explained by the frontier molecular orbital interactions between the reactive intermediates and the nucleophiles such as the amino or hydroxyl groups of nucleosides. Furthermore, longer oligonucleotides were synthesized not only by a manual operation but also by a DNA synthesizer. The utility of our new method was demonstrated by the successful synthesis of a base-labile modified oligodeoxyribonucleotide having 4-N-acetyldeoxycytidine residues. Finally, DNA 20-mers containing dA or dC could be synthesized in good yields by use of a combined reagent of 6-trifluoromethyl-1-hydroxybenzotriazole and benzimidazolium triflate.     

Ruthenium-catalyzed hydrogenation of alkynylstannanes with migration of the stannyl group

Molecular hydrogen adds to aliphatic and aromatic alkynylstannanes in the presence of a ruthenium catalyst, pushing the stannyl group to the adjacent carbon atom to give alpha-substituted vinylstannanes. This is the first achievement of hydrogenation of alkynylstannanes, which is applicable also to the deuteration affording precursors for an important class of deuterium-labeled compounds.     

Photochemical ligation of DNA conjugates through anthracene cyclodimer formation and its fidelity to the template sequences

Anthracene readily forms photoadducts, anthracene dimers, and this photodimerization reaction has been well characterized. In general, however, the reaction requires close proximity and certain spatial alignment of both reaction partners. DNA could provide an ideal scaffold for accelerating the photocyclic addition. We synthesized a number of anthracene-DNA conjugates. The sequences of the conjugates, 5'AntODNn and 3'AntODNn (the length of methylene linkers: n = 3 or 6), were designed to bind adjacent sequences of the template with the anthracene units directed such that they stacked with each other. The conjugates were only dimerized in the presence of the template by light irradiation. The efficiency was affected by one-base displacement in the template sequence.