Synthesis, Characterization, and Crystal Structure of a (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) Complex with a Dinucleating Hexapyridine Ligand, 1,2-Bis[2-(bis(2-pyridyl)methyl)-6-pyridyl]ethane. The First Example of a Discrete (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) Complex with a Dinucleating Ligand

A mononucleating tripyridine ligand, 2-(bis(2-pyridyl)methyl)-6-methylpyridine (L(1)), and a dinucleating hexapyridine ligand, 1,2-bis[2-(bis(2-pyridyl)methyl)-6-pyridyl]ethane (L(2)), have been prepared. The reaction of a carbanion of 2,6-lutidine with 2-bromopyridine affords L(1) which is converted to L(2) quantitatively by treating with tert-butyllithium and 1,2-dibromoethane. (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) complexes [Fe(2)(O)(OAc)(2)(L(1))(2)](ClO(4))(2) (1) and [Fe(2)(O)(OAc)(2)L(2)](ClO(4))(2) (2) have been synthesized and characterized by means of infrared, UV/vis, mass, and M?ssbauer spectroscopies and by measuring magnetic susceptibility and cyclic voltammograms. All the spectral data are consistent with the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure in both 1 and 2. A relatively strong molecular ion peak at m/z 865 corresponding to [{Fe(2)O(OAc)(2)L(2)}(ClO(4))](+) in a FAB mass spectrum of 2 suggests the stabilization of the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure by L(2) in a solution state. The compound 2.DMF.2-PrOH.H(2)O, chemical formula C(44)Cl(2)Fe(2)H(51)N(7)O(16), crystallizes in the monoclinic space group C2/c with a = 22.034(6) ?, b = 12.595(5) ?, c = 20.651(7) ?, beta = 121.49(2) degrees, and Z = 4. The cation has 2-fold symmetry with the bridging oxygen atom on the 2-fold axis: Fe-(&mgr;-O) = 1.782(5) ?, Fe-O-Fe = 123.6(6) degrees, and Fe.Fe = 3.142(3) ?. The diiron(III) core structure of 2 seems to be stabilized by encapsulation of the ligand. Compound 2 is the first example of a discrete (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) complex with a dinucleating ligand.     

Side chain type ionic liquid crystalline polymers having high Preliminary communication molecular weight

Side chain type ionic liquid crystalline polymers having a 4-(1,3-dioxan-2-yl)pyridinium structure in their mesogenic side chain were synthesized. These polymers exhibited the smectic A phase. The molecular weights of these ionic liquid crystalline polymers are very high, e.g. for compound 7 - 2 M _w = 486 000.     

Efficient Synthesis of Polycyclic γ-Lactams by Catalytic Carbonylation of Ene-Imines via Nickelacycle Intermediates

The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)₃L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams.     

Intra-abdominal fat area is a predictor for new onset of individual components of metabolic syndrome: MEtabolic syndRome and abdominaL ObesiTy (MERLOT study)

Objective: To investigate the significance of intra-abdominal fat area (IAFA) on new onset of individual components of the metabolic syndrome: high blood pressure, dyslipidemia, or hyperglycemia. Methods: We conducted a longitudinal study using checkup data of a hospital from 1994 to 2010. Of 25,255 subjects, we examined 1,380 Japanese, who underwent computed tomography to measure IAFA and had no metabolic syndrome components at baseline. Results: During 3.6 years of the mean follow-up period, one of metabolic syndrome components occurred in 752 subjects. Of three components, high blood pressure was more prevalent. The multiple Cox regression analysis disclosed that IAFA is significantly associated with onset of metabolic syndrome components (HR: 1.05 per 10 cm², 95%CI: 1.03–1.07). This finding was independent of BMI, and significant even in non-obese individuals with body mass index <25 kg/m². Conclusions: MERLOT study demonstrates that IAFA is an independent predictor for new onset of individual components of the metabolic syndrome, even in non-obese healthy Japanese.     

New heterocyclic metallomesogens: synthesis,mesomorphic and thermal behaviours of Cu(II) complexes with 1,2,3-triazole-based Schiff bases ligands

Two series of new Cu(II) complexes derived from the reaction of copper acetate with the non-linear 1,2,3-triazole-based Schiff bases have successfully been synthesised. The structures of the ligands and its complexes were elucidated by elemental analysis, FT-IR, ¹H-NMR and UV–visible spectroscopic techniques. The differential scanning calorimetry and polarizing optical microscopy supported the anisotropic properties of uncoordinated ligands in which the focal conic fan-shaped texture and/or broken fan-shaped texture characteristics of respective SmA and SmC phases were recorded. However, not all of their corresponding Cu(II) complexes are mesogenic. Although the iodo-substituted ligands with even parity C₁₀H₂₉ to C₁₄H₃₃ are non-stable and exhibit SmA phase which is not reproducible, the ultimate Cu(II) complexes show exclusively stable SmA phase. This observation can be ascribed to the enhanced colinearity and molecular anisotropic by the presence of Cu-N and Cu-O coordination modes. On the other hand, the comparison studies show that different positions of ortho-hydroxyl group affect the mesomorphic and thermal behaviour of ligands and Cu(II) complexes.     

Stereoselective analysis of flecainide enantiomers using reversed‐phase liquid chromatography for assessing CYP2D6 activity

Stereoselective analyses of flecainide enantiomers were performed using reversed‐phase high‐performance liquid chromatography (HPLC) equipped with a polysaccharide‐based chiral column (Chiralpak AS‐RH) and fluorescence detector. Excitation and emission wavelengths were set at 300 and 370 nm, respectively. Flecainide enantiomers in serum and urine were extracted using diethyl ether. The mobile phase solution, comprising 0.1 m potassium hexafluorophosphate and acetonitrile (65:35, v/v), was pumped at a flow rate of 0.5 mL/min. The recoveries of flecainide enantiomers were greater than 94%, with the coefficients of variation (CVs) <6%. The calibration curves of flecainide enantiomers in serum and urine were linear in the concentration range 5–500 ng/mL and 0.75–15 µg/mL (r > 0.999), respectively. CVs in intra‐day and inter‐day assays were 1.8–5.8 and 3.4–7.5%, respectively. In a pharmacokinetic study, the ratios of (S)‐ to (R)‐flecainide (S/R ratio) in the area under the curve and the amount of flecainide enantiomers excreted in urine were lower in a subject carrying CYP2D6*10/*10 than in subjects carrying CYP2D6*1/*2. The S/R ratio of trough serum flecainide concentration ranged from 0.79 to 1.16 in patients receiving oral flecainide. The present HPLC method can be used to assess hepatic flecainide metabolism in a pharmacokinetic study and therapeutic drug monitoring. Copyright © 2014 John Wiley & Sons, Ltd.     

Weighted Counting of Inversions on Alternating Sign Matrices

We generalize the author’s formula (2011) on weighted counting of inversions on permutations to one on alternating sign matrices. The proof is based on the sequential construction of alternating sign matrices from the unit matrix which essentially follows from the earlier work of Lascoux-Schützenberger (1996).

     

Synthesis of Adamantane Derivatives. Xxiii. Facile Photo-Ring-Cleavage of 4-Homoadamantanone to Bicyclo[3.3.1] -Nonan-3 -Endo-Acetate

Type I (α-) and II cleavages are two of the best known photochemical processes of alkanone.² Extensive and intensive investigations have been done on both types of reactions in order to clarify the influence of structural changes on the reactivity, specificity, and efficiency of photoreactions of alkanones.³ The type I cleavage of medium-ring alkanones is believed to produce a radical pair, the fate of which will be determined by the ready formation of transition states for transfer of Ha, Hb, and recyclization. We now wish to report