Minimization of erase-band in shingled PMR with asymmetric writer

To make the write-field much stronger with sharper cross-track field gradient in Shingled perpendicular Magnetic Recording (SMR), we have successfully developed asymmetric SMR heads with one-side shield design. Using these heads, higher track density capability on the shielded-side was demonstrated, which came from narrower erase-band width at shielded side.     

Synthesis and Systematic Structural Analysis of Cationic Half-Sandwich Ruthenium Chalcogenocarbonyl Complexes

Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H₂IMes)(CNCH₂Ts)][BAr^F₄] (Cp=η⁵-C₅H₅⁻; H₂IMes=1,3-dimesitylimidazolin-2-ylidene; Ar^F=3,5-(CF₃)₂C₆H₃). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O<S<Se<Te. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability.     

Highly active polymeric organocatalyst: Chiral ionic polymers prepared from 10,11‐didehydrogenated cinchonidinium salt

Since few examples of 10,11‐didehydrogenated (3‐ethynyl) cinchona alkaloids have been utilized as organocatalysts in asymmetric reaction, we synthesized 10,11‐didehydrogenated cinchonidine. The 3‐vinyl group of cinchonidine was transformed into a 3‐ethynyl functionality. Based on the resulting 10,11‐didehydrogenated cinchonidine, the corresponding quaternary ammonium salt and its dimers were prepared. The ion‐exchange reaction between the quaternary ammonium salt and sodium sulfonate produced the quaternary ammonium sulfonate as a stable ionic compound. Chiral ionic polymers were then synthesized by the ion‐exchange polymerization of the 10,11‐didehydrogenated cinchonidinium salt dimer and a disulfonate. The chiral ionic polymers were found to be capable of efficiently catalyzing the asymmetric alkylation of N‐(diphenylmethylene)glycine tert‐butyl ester. The enantioselectivities obtained with the polymeric catalysts were higher than those obtained with the corresponding monomeric catalyst. Dimers of 10,11‐didehydrogenated cinchonidinium salts were prepared. Treatment of the dimer with disodium disulfonate gave the chiral ionic polymers, which showed high catalytic activity in asymmetric benzylation of N‐(diphenylmethylen)glycine tert‐butyl ester. The polymeric catalysts were reused several times without the loss of catalytic activity. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 621–627     

Abnormal Li diffusion in β-LiGa by the formation of defect complex

The diffusion coefficients of Li in the NaTl-type Li intermetallic compound of β-LiGa have been measured by using a short-lived radioactive diffusion tracer. As the tracer, the α-emitting radioisotope of ⁸Li delivered as the energetic and pulsed beam from Tokai Radioactive Ion Accelerator Complex (TRIAC) was implanted into the β-LiGa compounds with the composition in the range of about 43 to 54 at.% Li. By analyzing the time-dependent yields of the α-particles measured according to the repetition cycle of the beam, the tracer diffusion coefficients were extracted over the wide range of Li composition. Abnormal composition-dependence of Li diffusion coefficients in β-LiGa was observed; the stoichiometric β-LiGa showed the highest diffusivity of Li. By referring to the composition-dependent diffusivity of Li in the iso-structural β-LiAl and β-LiIn, we could identify the abnormal diffusion of Li in very Li-poor composition of β-LiGa. The anomaly has been discussed qualitatively in terms of the formation of defect complex and the interaction between the constitutional defects.     

A novel derivatization reagent possessing a bromoquinolinium structure for biological carboxylic acids in HPLC‐ESI‐MS/MS

A novel bromoquinolinium reagent, i.e. 1‐(3‐aminopropyl)‐3‐bromoquinolinium bromide (APBQ), was synthesized for the analysis of carboxylic acids. A simple and practical precolumn derivatization procedure using the APBQ in RP chromatography and MS (HPLC‐MS) has been developed using bile acids and free fatty acids, as the representative carboxylic acids in biological samples. The APBQ efficiently reacted with carboxylic acids at 60°C for 60 min in the presence of N,N‐dicyclohexylcarbodiimide and pyridine as the activation reagents. Because the APBQ possesses a bromine atom in the structure, the identification of a series of carboxylic acids was easily achieved due to the characteristic bromine isotope pattern in the mass spectra. The APBQ also has a quaternary amine structure, thus the positively charged derivatives are predominate for the highly sensitive detection of carboxylic acids. The APBQ was successfully applied to the selective determination of biological carboxylic acids in human plasma. The bile acids (chenodeoxycholic acid and deoxycholic acid) and several saturated (stearic acid and palmitic acid) and unsaturated free fatty acids (oleic acid and linoleic acid) were reasonably determined by HPLC‐MS under the proposed procedure. Based on the results of analyses of human plasma and saliva, the proposed procedure using APBQ seems to be applicable for the qualitative and quantitative analyses of a series of carboxylic acids in biological samples.     

Cubic phases of binary systems of 4′-n-tetradecyloxy-3′-nitrobiphenyl-4-carboxylic acid (ANBC-14)-n-alkane

The phase behaviour of the binary systems 4′- ⁿ -tetradecyloxy-3′-nitrobiphenyl-4-carboxylic acid (ANBC-14)- ⁿ -alkane ( ⁿ -tetradecane or ⁿ -hexadecane) was investigated by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. The phase behaviour was a function of temperature ( ^T ) and the effective carbon number of the system ( ^n*), where ^n* involves carbon atoms both from the alkoxy group of ANBC-14 and from the ⁿ -alkane added. ANBC-14 shows no cubic phase, but the addition of ⁿ -alkane induced cubic phases when ^n*≧c. 15. An interesting point is that the type of cubic phase is ^Ia 3 ^d for 15^≦n*≦17, while an ^Im 3 ^m type is formed for 18^≦n*≦20. Furthermore, for ^n* = 22, two types of cubic phase, one with ^Im 3 ^m symmetry in the low temperature region and the other with ^Ia 3 ^d in the high temperature region, were observed both on heating and cooling. The phase diagram with respect to ^T and ^n* is very similar to that of pure one-component ANBC- ⁿ , which is a function of ^T and the number of carbon atoms in the alkoxy group ⁿ .     

Synthesis of 8-Methoxycarbonyloctylβ-Glycosides of Tri-and Tetrasaccharides Related to Schizophyllan and Neoglycoproteins Therefrom

Abstract

The 8-methoxycarbonyloctyl β-glycosides of the trisaccharides O-β-d-Glcp-(1 → 6)- O-β-d-Glcp-(1 → 3)-d-Glcp and O-β-d-Glcp-(1 → 3)-O-[β-d -Glcp-(1 → 6)]-d-Glcp and of the tetrasaccharide O-β-d-Glcp-(1 → 3)-O-[β-d-Glcp-(1 → 6)]-O-β-d-Glcp-(1 → 3)-d-Glcp, corresponding to the fragments of schizophyllan, have been synthesized by using mono- to tetrasaccharide 1-thioglycosides as glycosyl donors, each bearing a participating benzoyl group in the 2-position, and N-iodosuccinimide and silver triflate as promoter. Saponification of the tri- and tetrasaccharide β-glycosides, followed by attachment to bovine serum albumin of the resulting sugar derivatives having a carboxyl group at the aglycon terminal, provided neoglycoproteins for immunological studies of the polysaccharide.     

Ni‐Catalyzed [4+3+2] Cycloaddition of Ethyl Cyclopropylideneacetate and Dienynes: Scope and Mechanistic Insights

A detailed study of the Ni‐catalyzed [4+3+2] cycloaddition reaction between ethyl cyclopropylideneacetate and dienynes has been conducted, resulting in the development of a new method for the synthesis of compounds containing nine‐membered rings. We studied the reactivity of various dienynes, together with their substituent and conformational effects. The mechanism of the reaction was probed by examining the stoichiometric reactions of the Ni complexes and dienynes.     

7,7,8,8‐Tetraaryl‐o‐quinodimethane Stabilized by Dibenzo Annulation: A Helical π‐Electron System That Exhibits Electrochromic and Unique Chiroptical Properties

When two benzene rings are fused to a tetraaryl‐o‐quinodimethane skeleton, sterically hindered helical molecules 1 acquire a high thermodynamic stability. Because the tetraarylbutadiene subunit contains electron‐donating alkoxy groups, 1 undergo reversible two‐electron oxidation to 2 ²⁺, which can be isolated as deeply colored stable salts. Intramolecular transfer of the point chirality (e.g., sec‐butyl) on the aryl groups to helicity induces a diastereomeric preference in dications 2 b ²⁺ and 2 c ²⁺, which represents an efficient method for enhancing circular‐dichroism signals. Thus, those redox pairs can serve as new electrochiroptical response systems. X‐ray analysis of dication 2 ²⁺ revealed π–π stacking interaction of the diarylmethylium moieties, which is also present in solution. The stacking geometry is the key contributor to the chirosolvatochromic response.     

Selective hydrogen peroxide oxidation of sulfides to sulfoxides or sulfones with MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions

Selective oxidation of sulfides to sulfoxides and sulfones with hydrogen peroxide under organic solvent-free conditions was demonstrated by the MWW-type titanosilicate zeolite catalyst. Sulfides were oxidized smoothly to give sulfoxides with good selectivities at ambient temperature using 1.0–1.2 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst. Especially, the Ti-MWW with an interlayer-expanded structure (Ti-IEZ-MWW) catalyst showed high activity with good chemoselectivity for the oxidation of various sulfides. The catalyst is recyclable for at least five cycles, and the only byproduct is water. Sulfides were directly oxidized to give sulfones in high yields by 2.5 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions.