Survey meter combining CVD diamond and silicon detectors for wide range of dose rates and high accumulated doses

We have developed a prototype of a survey meter combining a CVD diamond detector and silicon detectors to appropriately take temporal measurements of γ-ray radiations over a wide range of the dose rates and to measure high accumulated doses of γ-ray radiations. In order to carry out this, at first, we have studied the radiation hardness of diamond detectors suitably fabricated with high-quality single-crystalline CVD diamond films to confirm that such CVD diamond detectors have greatly superior radiation hardness, compared with commercially available silicon detectors. It is evidenced that the performance of the CVD diamond detector did not significantly change even after heavy γ-ray irradiation of 0.7 MGy while the silicon detectors have a remarkable increase in the dark current, a detection peak shift to the low energy side, and a decrease in detection counts for 5.486-MeV α particles. Due to a size limitation of the CVD diamond detector, such a CVD diamond detector was combined with six commercially available silicon detectors to fabricate a survey meter which can appropriately work under severe irradiation conditions, or, at accumulated doses larger than at least 0.5 MGy and which can cover a wide range of the dose rates from 1 μGy/h to at least 1 kGy/h. The prototype survey meter had a practically useful linearity in this dose rate range. Thus, we have confirmed that such a diamond-Si combined survey meter can be put into practical use.     

In vivo assessment of the permeability of the blood--brain barrier and blood-retinal barrier to fluorescent indoline derivatives in zebrafish

ABSTRACT: BACKGROUND: Successful delivery of compounds to the brain and retina is a challenge in the development of therapeutic drugs and imaging agents. This challenge arises because internalization of compounds into the brain and retina is restricted by the blood--brain barrier (BBB) and blood-retinal barrier (BRB), respectively. Simple and reliable in vivo assays are necessary to identify compounds that can easily cross the BBB and BRB. METHODS: We developed six fluorescent indoline derivatives (IDs) and examined their ability to cross the BBB and BRB in zebrafish by in vivo fluorescence imaging. These fluorescent IDs were administered to live zebrafish by immersing the zebrafish larvae at 7--8 days post fertilization in medium containing the ID, or by intracardiac injection. We also examined the effect of multidrug resistance proteins (MRPs) on the permeability of the BBB and BRB to the ID using MK571, a selective inhibitor of MRPs. RESULTS: The permeability of these barriers to fluorescent IDs administered by simple immersion was comparable to when administered by intracardiac injection. Thus, this finding supports the validity of drug administration by simple immersion for the assessment of BBB and BRB permeability to fluorescent IDs. Using this zebrafish model, we demonstrated that the length of the methylene chain in these fluorescent IDs significantly affected their ability to cross the BBB and BRB via MRPs. CONCLUSIONS: We demonstrated that in vivo assessment of the permeability of the BBB and BRB to fluorescent IDs could be simply and reliably performed using zebrafish. The structure of fluorescent IDs can be flexibly modified and, thus, the permeability of the BBB and BRB to a large number of IDs can be assessed using this zebrafish-based assay. The large amount of data acquired might be useful for in silico analysis to elucidate the precise mechanisms underlying the interactions between chemical structure and the efflux transporters at the BBB and BRB. In turn, understanding these mechanisms may lead to the efficient design of compounds targeting the brain and retina.     

Chromatic aberration free liquid crystal adaptive optics for flood illuminated retinal camera

A high-resolution, flood-illumination retinal camera using liquid crystal (LC) adaptive optics (AO) is presented. The retinal camera uses light at 780 nm for ocular aberration measurement while light at 655 nm and 593 nm for retinal imaging. In order to avoid chromatic aberrations due to wavelength dependence of LC, we adopt an open-loop technique, in which dynamic correction of aberrations is applied only to the imaging light. A compensation pattern projected on the LC wavefront corrector is adjusted to provide phase wrapping of 2 π for illumination light. We confirmed feasibility of this technique by performing in vivo retinal imaging experiments. Photoreceptors were clearly revealed at both imaging light at 655 nm and 593 nm. Feasibility of the technique was also supported by comparison of the retinal images taken by the present open-loop technique with those taken by the conventional closed-loop one and by analysis of the spatial distribution of the photoreceptors.     

Coherent storage of photoexcited triplet states using 29Si nuclear spins in silicon

Pulsed electron paramagnetic resonance spectroscopy of the photoexcited, metastable triplet state of the oxygen-vacancy center in silicon reveals that the lifetime of the m(s)=±1 sublevels differs significantly from that of the m(s)=0 state. We exploit this significant difference in decay rates to the ground singlet state to achieve nearly ~100% electron-spin polarization within the triplet. We further demonstrate the transfer of a coherent state of the triplet electron spin to, and from, a hyperfine-coupled, nearest-neighbor (29)Si nuclear spin. We measure the coherence time of the (29)Si nuclear spin employed in this operation and find it to be unaffected by the presence of the triplet electron spin and equal to the bulk value measured by nuclear magnetic resonance.     

Highly enantioselective synthesis of silahelicenes using Ir-catalyzed [2+2+2] cycloaddition

Silahelicenes, which contain two silole moieties in a helically chiral structure, were synthesized by a chiral Ir-catalyzed intermolecular [2+2+2] cycloaddition of tetraynes with diynes along with a Ni-mediated intramolecular [2+2+2] cycloaddition. The photophysical properties of the obtained highly enantiomerically enriched silahelicenes (up to 93% ee) were also measured.     

A vapoluminescent Eu-based metallo-supramolecular polymer

An Eu-based metallo-supramolecular polymer (polyEu) was prepared by self-assembly coordination polymerization. Unique vapoluminescence property of polyEu triggered by acid-base vapor was found and a photoluminescence display in switchable imaging by acid-base vapor was fabricated.     

Fluorescence imaging of potassium ions in living cells using a fluorescent probe based on a thrombin binding aptamer-peptide conjugate

When a biotinylated FRET probe based on a peptide-thrombin binding aptamer conjugate was introduced together with streptavidin and biotinylated nuclear export signal peptide into HeLa cells, the resulting ternary complex enabled visualization of K(+) concentration changes in the cell.     

Efficient dynamic kinetic resolution of racemic secondary alcohols by a chemoenzymatic system using bifunctional iridium complexes with C-N chelate amido ligands

The combined catalyst system of bifunctional amidoiridium complexes derived from benzylic amines with CALB was found to provide a range of chiral acetates from racemic secondary alcohols in excellent yields with nearly perfect enantioselectivities via dynamic kinetic resolution.     

FMO‐MD Simulations on the Hydration of Formaldehyde in Water Solution with Constraint Dynamics

Full‐quantum mechanical fragment molecular orbital‐based molecular dynamics (FMO‐MD) simulations were applied to the hydration reaction of formaldehyde in water solution under neutral conditions. Two mechanisms, a concerted and a stepwise one, were considered with respect to the nucleophilic addition and the proton transfer. Preliminary molecular orbital calculations by means of polarized continuum model reaction field predicted that the hydration prefers a concerted mechanism. Because the calculated activation barriers were too high for free FMO‐MD simulations to give reactive trajectories spontaneously, a More O’Ferrall–Jencks‐type diagram was constructed from the statistical analysis of the FMO‐MD simulations with constraint dynamics. The diagram showed that the hydration proceeds through a zwitterionic‐like (ZW‐like) structure. The free energy changes along the reaction coordinate calculated by means of the blue moon ensemble for the hydration and the amination of formaldehyde indicated that the hydration proceeds through a concerted process through the ZW‐like structure, whereas the amination goes through a stepwise mechanism with a ZW intermediate. In inspection of the FMO‐MD trajectories, water‐mediated cyclic proton transfers were observed in both reactions on the way from the ZW‐like structure to the product. These proton transfers also have an asynchronous character, in which deprotonation from the nucleophilic oxygen atom (or nitrogen atom for amination) precedes the protonation of the carbonyl oxygen atom. The results showed the strong advantage of the FMO‐MD simulations to obtain detailed information at a molecular level for solution reactions.