Application of magnetic Compton scattering for spin‐specific magnetic hysteresis measurement

An application of magnetic Compton scattering as a new tool to measure a spin‐specific magnetic hysteresis (SSMH) loop is introduced and its validity demonstrated. The applied magnetic field dependence of the integrated intensity of magnetic Compton scattering spectra, which reflect only the spin‐dependent magnetic properties of magnetically active electrons, was interpreted as the spin‐specific hysteresis. The spin magnetization of amorphous Tb₃₃Co₆₇ film was observed and its SSMH loop exhibited qualitative agreement with the ordinal magnetic hysteresis loop measured using a conventional vibrating sample magnetometer.     

RA‐XXV and RA‐XXVI,Bicyclic Hexapeptides from Rubia cordifolia L.: Structure,Synthesis, and Conformation

Two RA‐series bicyclic hexapeptides, RA‐XXV ( 4 ) and RA‐XXVI ( 5 ), which have no N‐methyl group at Tyr‐5, were isolated from the roots of Rubia cordifolia L. Their amino acid compositions and sequences were determined by interpretation of MS, and 1D and 2D NMR data and their relative structures were elucidated by XRD analysis of 4 and RA‐XXVI acetate ( 6 ). The absolute stereochemistry of 4 was established by the total synthesis of 4 , and that of 5 , by the chemical correlation with 4 . Peptides 4 and 5 exhibited cytotoxicity toward human promyelocytic leukemia HL‐60 (IC₅₀=0.062 and 0.066 μm , respectively) and human colonic carcinoma HCT‐116 (IC₅₀=0.028 and 0.051 μm , respectively) cell lines. Analysis of the conformational structures of 4 and 6 in the crystalline state and those of 4 and 5 in solution revealed that the N‐methyl group at Tyr‐5 functions to make this series of peptides preferentially adopt the active conformation.     

Universal Coding for Classical-Quantum Channel

We construct a universal code for a stationary and memoryless classical-quantum channel as a quantum version of the universal coding by Csiszár and Körner. Our code is constructed utilizing a combination of irreducible representations, a decoder introduced through the quantum information spectrum, and the packing lemma.     

Reversible O-O Bond Scission of Peroxodiiron(III) to High-Spin Oxodiiron(IV) in Dioxygen Activation of a Diiron Center with a Bis-tpa Dinucleating Ligand as a Soluble Methane Monooxygenase Model

The conversion of peroxodiiron(III) to high-spin S = 2 oxodiiron(IV) via reversible O-O bond scission in a diiron complex with a bis-tpa dinucleating ligand, 6-hpa, has been characterized by elemental analysis; kinetic measurements for alkene epoxidation; cold-spray ionization mass spectrometry; and electronic absorption, M?ssbauer, and resonance Raman spectroscopy to gain insight into the O(2) activation mechanism of soluble methane monooxygenases. This is the first synthetic example of a high-spin S = 2 oxodiiron(IV) species that oxidizes alkenes to epoxides efficiently. The bistability of the peroxodiiron(III) and high-spin S = 2 oxodiiron(IV) moieties is the key feature for the reversible O-O bond scission.     

Imination of Sulfides and Sulfoxides with Sulfonylimino‐λ3‐Bromane under Mild,Metal‐Free Conditions

Exposure of sulfides and sulfoxides to trifluoromethanesulfonylimino(aryl)‐λ³‐bromane in dichloromethane at 0 °C results in a facile transfer of the sulfonylimino group to sulfur atoms and affords N‐triflylsulfilimines and ‐sulfoximines in high yields under transition‐metal‐free conditions. Imination of (R)‐methyl p‐tolyl sulfoxide proceeded with predominant retention of configuration at the stereogenic sulfur center. The Hammett plot afforded ρ values of ?0.58 for para‐substituted thioanisoles and ?0.49 for their equivalent sulfoxides, which suggests a buildup of positive charge on the sulfur atoms of sulfides and sulfoxides in the transition state. Calculations suggest a bimolecular nucleophilic‐substitution mechanism on the negatively charged nitrogen atom of the sulfonylimino‐λ³‐bromane, which involves the attack of a sulfide from the opposite side to bromine(III).     

Mechanism of enantioselective C-C bond formation with bifunctional chiral ru catalysts: NMR and DFT study

The mechanism of Michael addition reactions of 1,3-dicarbonyl compounds to cyclic enones catalyzed by bifunctional Ru catalysts bearing N-sulfonylated (R,R)-DPEN ligands (DPEN = (R,R)-1,2-diphenylethylenediamine) was studied by NMR and DFT computational analyses. NMR investigation of the stoichiometric reactions of chiral amido Ru complexes, Ru(N-sulfonylated dpen)(η(6)-arene) 1a-c, with dimethyl malonate 2 and β-keto ester 3 revealed that at decreased temperatures deprotonation proceeds in a stereoselective manner to provide amine complexes. The reaction with malonic ester 2 provided exclusively C-bound amino Ru complexes 6a,c, while the reaction of β-keto ester 3 gave an equilibrium mixture of rapidly interconverting C- and O-bound complexes. The structures of C-bound Ru complex 6c and O-bound Ru complex 9c were determined by single crystal X-ray analysis. A computational study showed that the enatioselective C-C bond formation proceeds through intermediate formation of chelating ion pairs that coordinate a molecule of enone via the Ru metal center producing a highly organized environment for the C-C bond formation, yielding selectively only one enantiomer of the product. Systematic study of a series of the catalyst-substrate combinations revealed that the experimentally observed sense of enantioselection was consistently explained by computational analysis. The tendency of increasing ee with the bulk of the coordinated arene in Ru complex is reproduced computationally by changes in the difference of either ZPPE-corrected energies or Gibbs free energies for S- and R-pathways.     

Pd- and Cu-catalyzed one-pot multicomponent synthesis of hetero α,α'-dimers of heterocycles

A novel palladium- and copper-catalyzed one-pot multicomponent synthesis of hetero α,α'-dimers of heterocycles via Sonogashira coupling and double cyclization cascade involving imine formation has been developed. This reaction cascade proceeded under mild conditions, providing a powerful synthetic tool for the assembly of π-conjugated systems with a combination of palladium-catalyzed post-direct C-H bond arylations.     

Determination of nitrite, nitrate, bromide, and iodide in seawater by ion chromatography with UV detection using dilauryldimethylammonium-coated monolithic ODS columns and sodium chloride as an eluent

A method was developed for determination of inorganic anions, including nitrite (NO ₂ ^? ), nitrate (NO ₃ ^? ), bromide (Br^?), and iodide (I^?), in seawater by ion chromatography (IC). The IC system used two dilauryldimethylammonium bromide (DDAB)-coated monolithic ODS columns (50?×?4.6?mm i.d. and 100?×?4.6?mm i.d.) connected in series for separation of the ions. Aqueous NaCl (0.5?mol/L; flow rate, 3?mL/min) containing 5?mmol/L phosphate buffer (pH 5) was used as the eluent, and detection was with a UV detector at 225?nm. The monolithic ODS columns were coated and equilibrated with a 1-mmol/L DDAB solution (in H₂O/methanol, 90:10 v/v). The hydrophilic ions (NO ₂ ^? , NO ₃ ^? , and Br^?) were separated within 3?min and the retention time of I^? was 16?min. No interferences from matrix ions, such as chloride and sulfate ions, were observed in 35?‰ artificial seawater. The detection limits were 0.6?μg/L for NO ₂ ^? , 1.1?μg/L for NO ₃ ^? , 70?μg/L for Br^?, and 1.6?μg/L for I^? with a 200-μL sample injection. The performance of the coated columns was maintained without addition of DDAB in the eluent. The IC system was successfully applied to real seawater samples with recovery rates of 94–108?% for all ions.

An unexpected disproportional reaction of 2H-azirines giving (1E,3Z)-2-aza-1,3-dienes and aromatic nitriles in the presence of nickel catalysts

An unprecedented nickel-catalysed disproportional reaction of 2,3-diaryl-2H-azirines forming azabutadienes and aromatic nitriles was discovered. This reaction involves the cleavage of two bonds of the 2H-azirine framework, which provides a novel type of transformation of 2H-azirines.     

Practical synthesis of aromatic nitriles via gallium-catalysed electrophilic cyanation of aromatic C-H bonds

A gallium-catalysed, direct cyanation reaction of aromatic and heteroaromatic C-H bonds with cyanogen bromide was developed as a practical synthetic method for the preparation of aromatic nitriles.