Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Gamma-ray spectroscopy of the neutron-rich Ni region through heavy-ion deep-inelastic collisions

Nuclei in the neutron-rich Ni region have been studied by γ-ray spectroscopy. Gamma-rays emitted from isomers, with T _1/2 > 1 ns, produced in heavy-ion deep-inelastic collisions were measured with an isomer-scope. The nuclear structure of the doubly magic ⁶⁸Ni and its neighbor ^69,71Cu is discussed on the basis of the shell model. Future experiments for more neutron-rich Ni nuclei are also viewed. Received: 1 May 2001 / Accepted: 4 December 2001     

Outflow refreshment angiography: A bright blood, bright static tissue technique

A new “bright blood” strategy, outflow refreshment imaging, is introduced in which a number of overlapping slices are excited in rapid succession. Flowing spins that refresh each overlapped slice portion contribute a bright signal. Additionally, static tissue in each non-overlapped slice portion also yields a bright signal. However, the flow/static contrast is comparable to that produced in inflow refreshment images, and angiograms can be generated by conventional maximum intensity projection processing. The dual ability to visualize angiograms and static tissue images is a major benefit of the strategy. Computer simulations of flow sensitivities and in vivo results are presented which compare the outflow and inflow refreshment imaging strategies.     

Anisotropic giant magnetoresistance originating from the π-d interaction in a molecule

We synthesized TPP[Fe^III(Pc)(CN)₂]₂, PTMA_x[Fe^III(Pc)(CN)₂]·y(MeCN), and PXX [Fe^III(Pc)(CN)₂], a new series of charge-transfer salts containing the axially-substituted phthalocyanine (Pc), [Fe^III(Pc)(CN)₂]⁻. In this molecular unit, the π conduction electron derived from the Pc-ring coexists with the d electron which is a potential source of a local magnetic moment. Therefore various phenomena associated with the interplay between local magnetic moments and conduction electrons are expected. We observed the giant negative magnetoresistance (GNMR) in all the three salts. The GNMR is highly anisotropic for the magnetic-field direction, and reflects the g-tensor anisotropy of the local magnetic moment in the [Fe^III(Pc)(CN)₂]⁻ unit. This indicates that the GNMR in these salts originates from the strong π-d interaction in the [Fe^III(Pc)(CN)₂]⁻ unit.     

Validation of a method for predicting the precision, limit of detection and range of quantitation in competitive ELISA.

The mathematical model for predicting the precision, limit of detection (LOD) and range of quantitation (ROQ) in a competitive enzyme-linked immunosorbent assay (ELISA) proposed by Hayashi et al. (Anal. Chem., 2004, 76, 1295) was validated. The model describes the relative standard deviation (RSD) of concentration estimates by the RSDs of pipetting volumes of analyte, enzyme-conjugated antigen, antibody and substrate solutions, and the standard deviation (SD) of inherent absorbances between the wells in an ELISA plate. For 6 kinds of direct competitive ELISA kits, the LOD and ROQ predicted by the model agreed well with those obtained by experiments with real samples. It was also confirmed that the model is applicable to the prediction of uncertainty that depends on the pipetting error of the viscous antiserum solution. The model was demonstrated to be useful for estimating the LOD and ROQ of competitive ELISA.     

Continuous removal of radiolytic products from TBP extraction systems

In the actinide separation process using TBP as extractant, hydrolytic and radiolytic reactions cause a gradual decomposition of the extractant, resulting in the formation of degradation products which can affect process performance adversely. The TBP diluent has to be cleaned from these degradation products before it is reused. This paper deals with a procedure for solvent cleanup, using a fourstage continuous contactor for increasing the scrubbing efficiency.     

Electron-active cyclotron resonance in p-doped InMnAs in high magnetic fields

We present a theoretical and experimental study of electron-active cyclotron resonance in p-doped InMnAs in high magnetic fields. Results are based on an 8-band Pidgeon–Brown model generalized to include finite k_z effects and s(p)–d exchange interaction between itinerant carriers and Mn d-electrons. The e-active transitions in the valence band in p-doped samples take place due to the nature of multiple valence bands (heavy and light holes). We have calculated the absorption spectra in high magnetic fields and identified optical transitions which contribute to the cyclotron resonance for both e-active and h-active polarizations. Calculations show agreement with experimental results.     

Quasi-monocyclic near-infrared pulses with a stabilized carrier-envelope phase characterized by noncollinear cross-correlation frequency-resolved optical gating.

Precise characterization of noncollinear optical parametric amplifier idler pulses that have bandwidths of more than an octave with a center wavelength at 990 nm was demonstrated. The method employed was cross-correlation frequency-resolved optical gating with broadband sum-frequency mixing to take advantage of the idler's angular dispersion. Compression to near the transform limit was achieved to produce quasi-monocyclic near-infrared pulses by use of a deformable membrane mirror.