Conversion of oxido-bridged dinuclear ruthenium complex to dicationic dinitrosyl ruthenium complex using proton and nitric oxide: completion of NO reduction cycle

The hydroxido-bridged dinuclear ruthenium complex 4, which is supported by Tp ligands, has been prepared from protonation of the oxido-bridged dinuclear ruthenium complex 3. Additional protonation of 4, affording the aqua-bridged dinuclear ruthenium complex 5 in situ, and subsequent treatment with NO gave rise to the dicationic dinitrosyl complex 2. These indicate completion of the NO reduction cycle on the dinuclear ruthenium complex.     

Amphiphilic polysaccharide nanogels as artificial chaperones in cell-free protein synthesis

Cell-free protein synthesis is a promising technique for the rapid production of proteins. However, the application of the cell-free systems requires the development of an artificial chaperone that prevents aggregation of the protein and supports its correct folding. Here, nanogel-based artificial chaperones are introduced that improve the folding efficiency of rhodanese produced in cell-free systems. Although rhodanese suffers from rapid aggregation, rhodanese was successfully expressed in the presence of the nanogel and folded to the enzymatically active form after addition of cyclodextrin. To validate the general applicability, the cell-free synthesis of ten water-soluble proteins was examined. It is concluded that the nanogel enables efficient expression of proteins with strong aggregation tendency.     

Gadolinium ethoxybenzyl diethylenetriamine pentaacetic acid-enhanced MR finding of radiation-induced hepatic injury: Relationship to absorbed dose and time course after irradiation

Purpose

To evaluate if Gd-EOB-DTPA-enhanced MRI could identify liver tissue damage caused by radiation exposure in patients undergoing external beam radiation therapy.

Materials and methods

We enrolled 11 patients who underwent Gd-EOB-DTPA-enhanced MRI during or after radiotherapy in which the radiation field included the liver. External beam radiotherapy was delivered through multiple fields using a 10-MV linear accelerator. The hepatobiliary phase images of Gd-EOB-DTPA-enhanced MRI were qualitatively evaluated for the presence of a decreased uptake of Gd-EOB-DTPA in the irradiated area in the liver. Next, signal intensity (SI) ratio of the irradiated area to the non-irradiated liver parenchyma was also calculated. The absorbed dose of the irradiated area in the liver was standardized using equivalent dose in 2 Gy fraction (EQD2) and biological effective dose (BED). The results of qualitative analysis were compared with EQD2 or BED, and linear regression analysis was performed between EQD2 or BED and SI ratio.

Results

Twenty-two irradiated areas were evaluated. Qualitative analysis revealed a decreased uptake of Gd-EOB-DTPA in 14 areas and no decreased uptake of Gd-EOB-DTPA in eight areas. The thresholds of EQD2 and BED causing a decreased uptake of Gd-EOB-DTPA were considered to be 24 to 29 Gy and 29 to 35 Gy, respectively. Quantitatively, SI ratio decreased as EQD2 or BED increased (r = 0.89, p < 0.001), and the inverse relationship between signal enhancement and the absorbed dose in the irradiated area was obtained. One area with EQD2 of 50 Gy and BED of 60Gy showed a slightly decreased uptake of Gd-EOB-DTPA on the 40th day but a clearly decreased uptake of Gd-EOB-DTPA on the 123rd day from initiation of radiotherapy.

Conclusions

Gd-EOB-DTPA-enhanced MRI described RLI as a decreased uptake of Gd-EOB-DTPA matching the irradiated area. The occurrence of this finding was significantly correlated with the absorbed dose of the irradiated area in the liver.     

Tuning of the methylimidazolium/imidazole balance in polycations for gene carrier

The chemical structure of methylated poly(1‐vinylimidazole) (PVIm‐Me) has been tuned for gene carrier properties, which are cell viability, the stability of its DNA polyion complexes, and gene expression. The resulting PVIm‐Me with lower methylation degree (6 and 20 mol%) exhibited no significant cytotoxicity, as compared with 40 mol% PVIm‐Me, in spite of the same concentration and chemical structure of positive charges. The DNA complex with 20 mol% PVIm‐Me stably retained the DNA, as compared with 6 or 40 mol% PVIm‐Me, which was examined by competitive exchange with dextran sulfate. As a result, the DNA complex with 20 mol% PVIm‐Me mediated most efficient gene delivery, where the resulting transfection activity was higher than that mediated by a positive control, poly(ethylenimine). These results suggest that the optimization of the balance of the methylimidazolium and the imidazole groups of PVIm‐Me is essential for gene carrier design. Copyright © 2014 John Wiley & Sons, Ltd.     

A 385–500 GHz SIDEBAND-SEPARATING (2SB) SIS MIXER BASED ON A WAVEGUIDE SPLIT-BLOCK COUPLER

We have developed a 385–500 GHz sideband-separating (2SB) mixer, which is based on a waveguide split-block coupler at the edge of the H-plane of the 508 μm × 254 μm (WR 2.0) waveguide, for the Atacama Large Millimeter/submillimeter Array (ALMA). An RF/LO coupler, which contains an RF quadrature hybrid, two LO couplers, and an in-phase power divider, was designed with the issue of mechanical tolerance taken into account. The RF/LO coupler was measured optically with a microscope and electrically with a submillimeter vector network analyzer. The image rejection ratio (IRR) and the single-sideband (SSB) noise temperature of the receiver using the RF/LO coupler have also been measured. The IRR was found to be larger than 8 dB and typically ∼ 12 dB in the 385–500 GHz band. The SSB noise temperature of this receiver is 80 K at the band center, which corresponds to 4 times the quantum noise limit (hf/k) in SSB, and 250 K at the band edges. An erratum to this article can be found at     

A Fixed-Tuned W-Band Waveguide SIS Mixer with 4.0-7.5 GHz IF

The design and performance of a fixed-tuned W-band SIS mixer with a wide band IF of 4.0-7.5 GHz is presented. Waveguide-to-stripline transition of the SIS mixer is designed using the lumped-gap-source port provided by HFSS^TM. Measured receiver noise temperature is less than 25 K in the frequency range of 95-120 GHz, with a minimum value of around 19 K achieved. Mixer noise temperature is determined to be about 8.5 K, which is around twice the quantum limit (i.e., 2hw/k). In spite of the high IF frequencies (f ₀ = 6 GHz), the performance of the SIS receiver is comparable or even superior to those of the best mechanically-tunable waveguide SIS receivers at low IF frequencies (f ₀ = 1.5 GHz). This result suggests that it is easy to design waveguide-to-stripline transitions without scale-model measurements.     

Chemical Dynamic Kinetic Resolution and S/R Interconversion of Unprotected α‐Amino Acids

Reported herein is the first purely chemical method for the dynamic kinetic resolution (DKR) of unprotected racemic α‐amino acids (α‐AAs), a method which can rival the economic efficiency of the enzymatic reactions. The DKR reaction principle can be readily applied for S/R interconversions of α‐AAs, the methodological versatility of which is unmatched by biocatalytic approaches. The presented process features a virtually complete stereochemical outcome, fully recyclable source of chirality, and operationally simple and convenient reaction conditions, thus allowing its ready scalability. A quite unique and novel mode of the thermodynamic control over the stereochemical outcome, including an exciting interplay between axial, helical, and central elements of chirality is proposed.     

Coexistence of superconductivity and itinerant-antiferromagnetism in CrRe alloys

Zero field Re NMR of CrRe alloy with more than 18%Re in superconducting state has been observed. The nuclear spin-lattice relaxation time (T₁) of Re in the vortex state increases exponentially with decreasing temperature as in the case of BCS superconductor. The result shows a coexistence of superconductivity and itinerant-electron antiferromagnetism.