Temperature dependence of the lattice locations of boron implanted in germanium

The β-NMR of the probe atom ¹²B implanted in In-doped germanium was measured as a function of temperature. As a result, three resonances were observed: sharp and broad resonances around the Larmor frequency and a resonance split by the electric quadrupole interaction. It was found that the appearance of the resonances is similar to the case of Si host (Izumikawa et al. Hyperfine Interact. 136/137:559–605, 2001). The quadrupole coupling constant for the split resonance was deduced as ∣eqQ/h∣ = 252(3) kHz under the assumption that it has <111> axial symmetry. And furthermore, assuming that the defect atom jumps thermally between the identical defect sites, the activation energy of the jump was deduced as 0.4 ± 0.1 eV.     

Electronic structure of substitutional nitrogen impurity in TiO 2 studied by the β-NMR method

In order to study the local electronic structure of nitrogen impurity in rutile TiO₂, we have measured double-quantum NMR spectra of short lived β-emitter ¹²N(I = 1, T _1/2 = 11 ms) implanted into a rutile single crystal by means of the β-NMR technique. The resonance line obtained at room temperature is well accounted for by the second order shift due to the quadrupole interaction at the oxygen substitutional site. The spectrum at 25 K has shown the other lines than the central diamagnetic line shifted by 10?15 kHz to both sides, which has been already shown in the previous data obtained with a different crystal orientation and an external field. The present results supports the existence of a paramagnetic state formed by the substitutional nitrogen impurities.     

Hyperfine anomalies of Sc isotopes (A = 44, 44 m, 46 and 47) in iron

Nuclear magnetic resonance on oriented nuclei (NMR-ON) on Sc isotopes (A = 44, 44 m, 46, 47) in Fe were performed. Using the known magnetic moments the magnetic hyperfine fields were determined. The hyperfine anomalies of various Sc were deduced; ⁴⁴Δ⁴⁷ = 0.0 (12) %, ^44mΔ⁴⁷ = 1.2 (4) %, ⁴⁶Δ⁴⁷ = 2.7 (8) %. The measured hyperfine anomalies are briefly discussed based on the shell model.     

Asymmetric Total Synthesis of ent‐Pyripyropene A

An asymmetric total synthesis of ent‐pyripyropene A was achieved by a convergent synthetic route. We used our originally developed Ti^III‐catalyzed radical cyclization to construct an AB‐ring portion that consisted of a trans‐decalin skeleton with five contiguous stereogenic centers. The coupling between the AB‐ring and the DE‐ring portions, and a subsequent C‐ring cyclization, led to the total synthesis of ent‐pyripyropene A. An evaluation of the insecticidal activity of ent‐pyripyropene A against two aphid species revealed that ent‐pyripyropene A was 35–175 times less active than naturally occurring pyripyropene A. This result indicated that the biological target of pyripyropene A recognizes the absolute configuration of pyripyropene A.     

Beta-NMR measurement of 58Cu in Si

The β-NMR study of short-lived nucleus ⁵⁸Cu (I ^π ?=?1^?+?, T _1/2?=?3.2 s) in Si has been performed. Spin polarization of ⁵⁸Cu induced by the charge exchange reaction of ⁵⁸Ni was observed in Si at 15 K. The ⁵⁸Cu magnetic moment $|\upmu[^{58}\mbox{Cu}]| = (0.46 \pm 0.03)\upmu_{\rm N}$ deduced from the β-NMR spectrum is consistent with the previous results on the laser spectroscopy. The present result shows that the ⁵⁸Cu nucleus is promising as a new nuclear probe for the microscopic study of Cu impurities in Si.     

Nuclear moments as a probe of electronic structure in material, exotic nuclear structure and fundamental symmetry

We report our studies in various fields of Physics through nuclear moments utilizing the β-NMR technique, including material sciences, nuclear structures and fundamental symmetries. Especially, we focus on the recent progress in the studies on the electronic structure in Pt through Knight shifts of various impurities, lattice locations of impurities, electric field gradients, the analysis of nuclear spin in terms of its components, anomaly in the spin expectation value for ⁹C-⁹Li mirror pair, the G-parity conservation law, and the Ramsey resonance on UCN for future neutron EDM measurements.     

Total Synthesis and Structure Elucidation of JBIR‐39: A Linear Hexapeptide Possessing Piperazic Acid and γ‐Hydroxypiperazic Acid Residues

The total synthesis and stereochemical structural elucidation of JBIR‐39, containing four nonproteinogenic piperazic acid (Piz) residues, is reported. The synthesis includes Sc(OTf)₃‐catalyzed acylation of a Piz(γ‐OTBS) derivative with piperazic acid chloride, providing the desired Piz‐Piz(γ‐OTBS) dipeptide in high yield without epimerization. After assembling two additional Piz moieties and (S)‐isoleucic acid at the N‐terminus, amidation with the (R)‐α‐methylserine ester at the C‐terminus, and deprotection afforded the desired (2R,8S)‐hexapeptide, which is the assumed structure of JBIR‐39. Although the spectral data of the (2R,8S)‐hexapeptide was not identical to JBIR‐39, further synthesis of three stereoisomers confirmed the stereochemical structure of JBIR‐39 to be (2S,6S,8S,11R,16S,21R,26S,27S).     

Priming type II polyketide synthases via a type II nonribosomal peptide synthetase mechanism

Benzoic acid priming of the enterocin and actinorhodin type II polyketide synthase complexes was accomplished in vitro via an unprecedented type II nonribosomal peptide synthetase-like mechanism involving the benzoate:acyl carrier protein (ACP) ligase EncN and the ACP EncC. The transfer of the aryl acid to the ACP is ATP-dependent, yet coenzyme A-independent, as characterized with radiolabeled substrates and protein mass spectrometry. Subsequent transport of the ACP-bound aryl group to the native enterocin and the aberrant actinorhodin ketosynthase chain length factor heterodimers was further demonstrated, thereby demonstrating the potential of this biocatalyst for engineering diverse aryl-primed aromatic polyketide agents.     

Hyperfine interaction of13O and23Mg implanted in Pt

The spin relaxation timeT ₁ for short-lived beta emitters¹³O and²³Mg implanted in Pt have been measured for the first time;T ₁T¹³O) = 2.90 ±0.65 Ks andT ₁ T(²³Mg) = 1665 ±140 Ks. The Knight shift for¹³O in Pt was measured at 300 K to beK(¹³O) = +(4.23 ±0.14) × 10^–3. In the case of¹³O, the Knight shift is unusually large and the relaxation time is unusually fast compared with other interstitial impurities in Pt. A KKR band-structure calculation reproduces the present large Knight shift fairly well.     

Hyperfine interaction of 25Al in α-Al2O3 and its quadrupole moment

A brief review is presented of recent work with the Precision Penning Trap Mass Spectrometer, formerly at MIT, now at Florida State University. This includes atomic mass comparisons using single trapped ions; mass comparisons using two simultaneously trapped ions alternated between large and small cyclotron radii; and measurement of the dipole moment of a molecular ion using the polarizability-induced shift in cyclotron frequency.