Cuboctahedral type Ib diamonds in ophiolitic chromitites and peridotites: the evidence for anthropogenic contamination

ABSTRACT

Here we present trace element compositions of synthetic diamonds, which show spectacular similarity with the compositions of metallic inclusions in type Ib cuboctahedral diamonds in ophiolitic chromitites and peridotites. The compositions of inclusions in synthetic and ophiolite diamonds closely correspond to Ni:Mn:Co?=?70:25:5 in wt.%, which is the most widely used catalyst for HPHT growth of synthetic diamonds in China. Thus, we claim for thorough reconsideration of diamonds in ophiolitic rocks and emphasize that most of them appear by anthropogenic contamination.     

Practical comparison of sensitivity and resolution between STMAS and MQMAS for Al

An experimental comparison of sensitivity and resolution of satellite transition (ST) MAS and multiple quantum (MQ) MAS was performed for ²⁷Al (I = 5/2) using several pulse sequences with a z-filter and SPAM, and two inorganic samples of kaolin (Al₂Si₂O₅(OH)₄) and glass (43.1CaO–12.5Al₂O₃–44.4SiO₂). Six pulse sequences of STMAS (double-quantum filter-soft pulse added mixing = DQF-SPAM, double-quantum filter = DQF, double-quantum = DQ) and MQMAS (3QMAS-z-filter = 3Qz, 3QMAS-SPAM = 3Q-SPAM, 5QMAS-z-filter = 5Qz) are employed. All experiments have been conducted utilizing a static field of 16.4 T (700 MHz for ¹H) and a rotor spinning frequency of 20 kHz. Dependence of S/N ratios as a function of radio frequency (r.f.) field strengths indicates that strong r.f. fields are essential to obtain a better S/N ratio in all experiments. High sensitivity is obtained in the following order: DQF-SPAM, DQF, DQ, 3QSPAM, and 3Qz, although the degree of sensitivity enhancement given by STMAS for glass is slightly smaller than that for kaolin. This might be due to the different excitation and conversion efficiencies of ST and MQ coherences as a function C_q values because quadrupolar interaction of the glass are widely distributed, or to motional broadening caused by framework flexibility in the structure of glass. With respect to resolution, the full widths at half maximum (FWHM) of F₁ projections of DQF-STMAS and 3QMAS spectra for kaolin are found to be comparable, which agrees with a simulated result reported in a literature. For glass, the STMAS possess slightly wider line widths than 3QMAS. However, because such a difference in line widths of STMAS and 3QMAS spectra is substantially small, we have concluded that STMAS and 3QMAS have comparable resolution for crystalline and non-crystalline materials.     

Log canonical thresholds of binomial ideals

We prove that the log canonical thresholds of a large class of binomial ideals, such as complete intersection binomial ideals and the defining ideals of space monomial curves, are computable by linear programming. Dedicated to Professor Toshiyuki Katsura on the occasion of his sixtieth birthday     

Enantioselective epoxidation of terminal alkenes to (R)- and (S)-epoxides by engineered cytochromes P450 BM-3

Cytochrome P450 BM-3 from Bacillus megaterium was engineered for enantioselective epoxidation of simple terminal alkenes. Screening saturation mutagenesis libraries, in which mutations were introduced in the active site of an engineered P450, followed by recombination of beneficial mutations generated two P450 BM-3 variants that convert a range of terminal alkenes to either (R)- or (S)-epoxide (up to 83 % ee) with high catalytic turnovers (up to 1370) and high epoxidation selectivities (up to 95 %). A biocatalytic system using E. coli lysates containing P450 variants as the epoxidation catalysts and in vitro NADPH regeneration by the alcohol dehydrogenase from Thermoanaerobium brockii generates each of the epoxide enantiomers, without additional cofactor.     

Exceptional cases of Terai’s conjecture on Diophantine equations

Let a, b, c be relatively prime positive integers such that a ^p  + b ^q  = c ^r for fixed integers p, q, r ≥ 2. Terai conjectured that the equation a ^x  + b ^y  = c ^z in positive integers has only the solution (x, y, z) = (p, q, r) except for specific cases. In this paper, we consider the case q = r = 2 and give some results related to exceptional cases.     

Methyl‐Selective α‐Oxygenation of Tertiary Amines to Formamides by Employing Copper/Moderately Hindered Nitroxyl Radical (DMN‐AZADO or 1‐Me‐AZADO)

Methyl‐selective α‐oxygenation of tertiary amines is a highly attractive approach for synthesizing formamides while preserving the amine substrate skeletons. Therefore, the development of efficient catalysts that can advance regioselective α‐oxygenation at the N‐methyl positions using molecular oxygen (O₂) as the terminal oxidant is an important subject. In this study, we successfully developed a highly regioselective and efficient aerobic methyl‐selective α‐oxygenation of tertiary amines by employing a Cu/nitroxyl radical catalyst system. The use of moderately hindered nitroxyl radicals, such as 1,5‐dimethyl‐9‐azanoradamantane N‐oxyl (DMN‐AZADO) and 1‐methyl‐2‐azaadamanane N‐oxyl (1‐Me‐AZADO), was very important to promote the oxygenation effectively mainly because these N‐oxyls have longer life‐times than less hindered N‐oxyls. Various types of tertiary N‐methylamines were selectively converted to the corresponding formamides. A plausible reaction mechanism is also discussed on the basis of experimental evidence, together with DFT calculations. The high regioselectivity of this catalyst system stems from steric restriction of the amine‐N‐oxyl interactions.     

High‐Pressure Synthesis of A2NiO2Ag2Se2 (A=Sr,Ba) with a High‐Spin Ni2+ in Square‐Planar Coordination

Square‐planar coordinate Ni²⁺ ions in oxides are exclusively limited to a low‐spin state (S=0) owing to extensive crystal field splitting. Layered oxychalcogenides A₂Ni^IIO₂Ag₂Se₂ (A=Sr, Ba) with the S=1 NiO₂ square lattice are now reported. The structural analysis revealed that the Ni²⁺ ion is under‐bonded by a significant tensile strain from neighboring Ag₂Se₂ layers, leading to the reduction in crystal field splitting. Ba₂NiO₂Ag₂Se₂ exhibits a G‐type spin order at 130 K, indicating fairly strong in‐plane interactions. The high‐pressure synthesis employed here possibly assists the expansion of NiO₂ square lattice by taking the advantage of the difference in compressibility in oxide and selenide layers.     

Synthesis of the cyclohexene segment of portimine

The synthesis of the cyclohexene segment of portimine, a marine cytotoxin from the dinoflagellate Vulcanodinium rugosum, was achieved. The route includes an acylation/aldol reaction from 3-ethoxycyclohex-2-enone to create the C3 center, the 1,4-addition of a vinyl group at C16, the diastereoselective dihydroxylation of the vinyl group to generate the C15 center, a vinylation/dehydration sequence to set up the diene moiety, and stepwise installation of the amino-group-substituted C1 unit.