Production of hyperpolarized nuclei for MRI

The project in producing the hyperpolarized ³He and ¹⁹F are addressed in pursuit of radiation free medical diagnosis. The program for production of the hyperpolarized ³He by the brute force method with the Pomeranchuk cooling and the rapid melting of the solid 3He started a few years ago, and is still on the way, while a new program for production of the hyperpolarized ¹⁹F by means of the PHIP (ParaHydrogen Induced Polarization) has just got started. Particular attention is placed upon a new idea of the hyperpolarization catalyst to be used for ¹⁹F.     

The Effect of Intramolecular Hydrogen Bonding on the Intensity and Frequency of OH Stretching Band in Alicyclic Substances

The change in intensity and frequency of O-H stretching band upon intramolecular hydrogen bonding was sufficiently examined for various proton acceptors of many alicyclic substances. The order of proton acceptors to bring about the intensity increase of constant degree is: Some discussions are given on these.     

N‐Heterocyclic Carbene Catalyzed Concerted Nucleophilic Aromatic Substitution of Aryl Fluorides Bearing α,β‐Unsaturated Amides

Concerted nucleophilic aromatic substitution (CS_NAr) has emerged as a powerful mechanistic manifold, in which nucleophilic aromatic substitution can proceed in one step without the need to form a Meisenheimer intermediate. However, all of the CS_NAr reactions reported thus far require a stoichiometric strong base or activating reagent, and no catalytic variants have yet been reported. Herein, we report an N‐heterocyclic carbene (NHC)‐catalyzed intramolecular cyclization of acrylamides that contain a 2‐fluorophenyl group on the nitrogen through a CS_NAr reaction. By using this catalytic method, it is possible to synthesize an array of quinolin‐2‐one derivatives, which are common structural motifs in pharmaceuticals and organic materials. DFT calculations unambiguously revealed that this reaction proceeds through the concerted nucleophilic aromatic substitution of aryl fluorides, in which a stereoelectronic σ (C_ipso‐C_β)→ σ*(C_ipso‐F) interaction critically contributes to the stabilization of the transition state for the cyclization.     

Preparation, characterization, and heat resistance studies of a holographic photopolymer based on SU-8 epoxy resin

A holographic photopolymer based on SU-8 epoxy resin as the binder and trimethylolpropane ethoxylate triacrylate as the monomer with an iodonium salt photoinitiator was studied. A diffraction efficiency of 93% and a refractive index modulation (Delta n) of 1.3 x 10(-2) were obtained from a 16 microm thick sample with write beam intensities of 50 mW/cm(2) at a wavelength of 514.5 nm, an exposure time of 60 s, and a postbaking at 65 degrees C for 1 h. The material exhibits good heat resistance in the range from 40 degrees C to 160 degrees C and long projected life.     

掺杂AS2S8非晶态薄膜波导的光阻断效应

实验研究了未掺杂和低浓度掺锡和掺磷的As2S8薄膜波导的光阻断效应,提供了三种样品的光阻断响应曲线、室温退激实验数据和光谱测试数据.结果表明,掺锡样品可以明显提升毫秒级响应的快过程恢复作用,同时还具有减少残留传输损耗的效果,掺磷的效果则相反.结合实验结果给出了分析讨论.     

Oxygen bombardment effects on average crystallite size of sputter-deposited ZnO films

Zinc oxide (ZnO) film was deposited on a glass substrate by rf magnetron sputtering with O₂/Ar as working gases. Structural properties of the films were characterized by XRD. Average crystallite size in the films was strongly dependent on both the gas flow ratio of O₂/Ar and rf-power at a constant deposition pressure. During the deposition, energetic species in the plasma were in situ monitored using optical emission spectroscopy. An inverse correlation was observed between the average crystallite size and the emission intensity ratio of I_O^∗/I_Ar. Bombardment of atomic oxygen to the growing surface played an important role in determining the average crystallite size in the films. The average crystallite size could be controlled by the emission intensity ratio of I_O^∗/I_Ar.     

Chiral cyclic [n]spirobifluorenylenes: carbon nanorings consisting of helically arranged quaterphenyl rods illustrating partial units of woven patterns

Chiral cyclic [n]spirobifluorenylenes consisting of helically arranged quaterphenyl rods, illustrating partial units of woven patterns, were designed and synthesized as a new family of carbon nanorings. The synthesis was accomplished by the Ni(0)-mediated Yamamoto-coupling of chiral spirobifluorene building blocks. The structures of the cyclic 3-, 4-, and 5-mers were determined by X-ray crystallographic analysis. These carbon nanorings exhibited a strong violet colored emission with high quantum yields in solution (95%, 93%, and 94% for 3-, 4-, and 5-mer, respectively). Other spectroscopic properties, including their chiroptical properties, were also investigated. The g-values for circularly polarized luminescence were found to be in the order of 10⁻³. Characteristic spiroconjugation induced by multiple (≧3) bifluorenyl units, for example the even-odd effect of the number of units in the matching of the signs of the orbitals, was also indicated by DFT calculations.

Chiral cyclic [n]spirobifluorenylenes consisting of helically arranged quaterphenyl rods, illustrating partial units of woven patterns, were designed and synthesized as a new family of carbon nanorings.     

Shimalactone Biosynthesis Involves Spontaneous Double Bicyclo-Ring Formation with 8π-6π Electrocyclization

Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark.     

A simple high‐performance liquid chromatography for the determination of linezolid in human plasma and saliva

Linezolid is an antimicrobial agent for the treatment of multiresistant Gram‐positive infections. A practical high‐performance liquid chromatography method was developed for the determination of linezolid in human plasma and saliva. Linezolid and an internal standard (o‐ethoxybenzamide) were extracted from plasma and saliva with ethyl acetate and analyzed on a Capcell Pak C₁₈ MG column with UV detection at 254 nm. The calibration curve was linear through the range 0.5–50 µg/mL using a 200 μL sample volume. The intra‐ and interday precisions were all <6.44% for plasma and 5.60% for saliva. The accuracies ranged from 98.8 to 110% for both matrices. The mean recoveries of linezolid were 80.8% for plasma and 79.0% for saliva. This method was used to determine the plasma and saliva concentrations of linezolid in healthy volunteers who were orally administered a 600 mg dose of linezolid. Our liquid–liquid extraction procedure is easy and requires a small volume of plasma or saliva (200 μL). This small volume can be advantageous in clinical pharmacokinetic studies, especially if children participate. Copyright © 2015 John Wiley & Sons, Ltd.     

Visible-light photocatalysis of ZnO deposited on nanoporous Au

ZnO deposited on nanoporous Au showed photocatalytic decomposition toward methyl orange under visible light, unlike ZnO sputtered on flat Au without a nanoporous structure. First-principles calculations suggested that the surface lattice disorder in nanoporous Au induced a band gap narrowing and a large built-in electric field in the adjacent ZnO, resulting in the visible-light photocatalytic response.