Direct Enantioselective Three‐Component Synthesis of Optically Active Propargylamines in Water

An enantioselective three‐component reaction of aldehydes, amines, and alkynes in water by using a bis(imidazoline)–Cu^I catalysts having a hydrophobic substituent and sodium dodecyl sulfate as a surfactant was developed. The reaction was applied to a broad range of aldehydes and alkynes to give optically active propargylamines with excellent yields (up to 99 %) and enantiomeric excesses (up to 99 % ee).     

Simplification of formulas for compression wave and oscillating flow in circular pipe

We had already obtained the analytical solutions for the compression wave and steady-state oscillating flow in a pipe with a circular cross section [Sato Y, Kanki H. Formulas for compression wave and oscillating flow in circular pipe. To be published in Appl Acoust [accepted 11 Sept. 2006]]. This work contains three key-components. The first key is to simplify the formulas using the unique mathematic technique without losing the accuracy. Simplifying the formulas is the one of the most important factors for formulas used in engineering use. The results will enable us to greatly reduce the work and computation costs. The second is to verify the flow distribution calculated by our formulas. The third is to study the possibility of application of our method to the analysis in turbulent flow region. Kawata et al. have represented the validity of one-dimensional quasi-analysis in turbulent flow region, using the method of D’Souza et al. and the shear viscosity. Therefore, in this paper the validity of the analysis in a turbulence region was verified by proving theoretically that the methods of D’Souza et al. and ours are intrinsically equivalent. The proof of equivalence was accomplished using the formulas simplified in this paper.     

Anomalous field dependence of muon Knight shift and line width in the singlet ground state compound PrCu2

We report on ZF and TF‐studies of PrCu₂ above the induced Jahn–Teller transition at 7.3 K. Generally a two‐component signal is found, one showing inhomogeneous the other one homogeneous, temperature dependent line broadening. In ZF the former component is well represented by a Gaussian Kubo–Toyabe function with \varDelta \simeq 6.5\,μs^-1 at 7.5 K, corresponding to a field width of 76 G. This is about 30 times larger than what is calculated to arise from the ¹⁴¹Pr‐nuclear dipole moments alone, pointing to strong hyperfine enhanced features. TF‐field scans at 12 K revealed that the enhancement is suppressed in external fields exceeding 1 kG. In parallel the Knight shift drops from very large values well above 10% at 100 G to shifts of the order of 1% above 1 kG. A scaling of the Knight shifts with the corresponding relaxation rates seems to imply that the strange field dependence below 1 kG is associated with the magnetic susceptibility of the muons’s nearest neighbour Pr³⁺‐ions, a result for which we have no explanation yet to offer. This revised version was published online in July 2006 with corrections to the Cover Date.     

Electrical control of the direction of spin accumulation

We are able to continuously change the direction of polarization of spin accumulation in a nonmagnetic metal by varying the currents injected by two ferromagnetic spin injectors. From measurements made at a distance from the injection area, we find a cosvarphi variation of the spin signal. This confirms that the angle of polarization of the nonlocal spin polarization with respect to the magnetization of the fixed spin detector is continuously varied as we change the injection currents. We give an explanation for the origin of this simple cosvarphi variation of the spin signal.     

Superconductivity in heavy fermion systems

The heavy fermion state in the f-electron systems is due to competition between the RKKY interaction and the Kondo effect. The typical compound is CeCu₆. To understand the electronic state, we studied the Fermi surface properties via the de Haas–van Alphen (dHvA) experiment and energy band calculation for CeSn₃,CeRu₂Si₂,UPt₃, and nowadays, transuranium compounds. Pressure is also an important technique to control the electronic state. The Néel temperature T_N decreases with increasing pressure P and becomes zero at the critical pressure for . The typical compound is an antiferromagnet CeRhIn₅, which we studied from the dHvA experiment under pressure. A change of the 4f-electronic state from localized to itinerant is realized at , revealing the first-order phase transition, together with a divergent tendency of the cyclotron mass at P_c. It is stressed that appearance of superconductivity in CeRhIn₅ is closely related to the heavy fermion state. It is also noted that the parity-mixed novel superconducting state might be realized in a pressure-induced superconductor CeIrSi₃ without inversion symmetry in the crystal structure.     

Absolute stereochemistries and total synthesis of (+)-arisugacins A and B, potent, orally bioactive and selective inhibitors of acetylcholinesterase

In the current studies, we used the Kakisawa-Kashman modification of the Mosher NMR method to determine the complete absolute stereochemistry of arisugacins. We also report the convergent total synthesis of (+)-arisugacins A and B by a sequence including (i) ruthenium complex-catalyzed asymmetric reduction of the cyclohexenone derivative; (ii) stereoselective construction of the arisugacin skeleton by a Knoevenagel-type reaction of an α,β-unsaturated aldehyde derivative with production of a 4-hydroxy-2-pyrone derivative as a key reaction; and (iii) stereoselective dihydroxylation to give the diol derivative, followed by deoxygenation. Accordingly, we defined the absolute structures of arisugacins A and B as 4a-(R),6a-(R),12a-(R), and 12b-(S). Finally, we characterized the bioactivities of the synthetic intermediates to understand the structure-activity relationships of the arisugacins.     

Detection of a metallo-beta-lactamase (IMP-1) by fluorescent probes having dansyl and thiol groups

A fluorescent probe for the detection of a metallo-beta-lactamase (IMP-1), N-[2-(5-dimethylaminonaphthalen-1-ylsulfonylamino)ethyl]-3- mercaptopropionamide (Dansyl-C2SH), 1, was designed based on combining the inhibitory function of mercaptocarboxylate and a fluorophore. The binding of 1 to IMP-1 was investigated by fluorescence spectroscopy. Compound 1 can act as fluorescent probe for detecting IMP-1 selectively.     

Parallel generation of quadripartite cluster entanglement in the optical frequency comb

Scalability and coherence are two essential requirements for the experimental implementation of quantum information and quantum computing. Here, we report a breakthrough toward scalability: the simultaneous generation of a record 15 quadripartite entangled cluster states over 60 consecutive cavity modes (Q modes), in the optical frequency comb of a single optical parametric oscillator. The amount of observed entanglement was constant over the 60 Q modes, thereby proving the intrinsic scalability of this system. The number of observable Q modes was restricted by technical limitations, and we conservatively estimate the actual number of similar clusters to be at least 3 times larger. This result paves the way to the realization of large entangled states for scalable quantum information and quantum computing.     

de Haas–van Alphen effect in strongly correlated electron systems

We present the Fermi surface properties in strongly correlated electron systems of rare earth and uranium compounds via de Haas–van Alphen experiments. The conduction electrons with large cyclotron effective masses over 100m₀ (m₀: rest mass of an electron) are detected in CeRu₂Si₂, CeCoIn₅ and UPt₃. These electrons move slowly in the crystal. The topology of the Fermi surface and the cyclotron mass are compared to those of energy band calculations.     

Multifunctional Core–Shell Silica Nanoparticles for Highly Sensitive 19F Magnetic Resonance Imaging

¹⁹F magnetic resonance imaging (¹⁹F MRI) is useful for monitoring particular signals from biological samples, cells, and target tissues, because background signals are missing in animal bodies. Therefore, highly sensitive ¹⁹F MRI contrast agents are in great demand for their practical applications. However, we have faced the following challenges: 1) increasing the number of fluorine atoms decreases the solubility of the molecular probes, and 2) the restriction of the molecular mobility attenuates the ¹⁹F MRI signals. Herein, we developed novel multifunctional core–shell nanoparticles to solve these issues. They are composed of a core micelle filled with liquid perfluorocarbon and a robust silica shell. These core–shell nanoparticles have superior properties such as high sensitivity, modifiability of the surface, biocompatibility, and sufficient in vivo stability. By the adequate surface modifications, gene expression in living cells and tumor tissue in living mice were successfully detected by ¹⁹F MRI.