尖晶石纳米催化剂应用于烯丙醇多相氧化制烯丙醛或烯丙酮

使用共沉淀法通过Ru对MeFe2O4的同晶取供制备了纳米级MnFe1.95Ru0.05O4催化剂。在通过过渡金属进一步改性该催化剂的过程中，发现MnFe1.95Ru0.05O4的催化剂性能优异于文献报道的其他多相醇氧化催化剂，XRD测试表明该催化剂仍保持尖晶石结构。该纳米催化剂能有效地将不同烯丙醇类氧化成烯丙醛类或烯丙酮类，与文献报道的其他多相氧化催化体系相比，该催化剂具有更高的活性转换数。借助于EXAFS等表征结果和1－辛醇与4－辛醇的竞争反应，判断出单核的Ru类反应的活性中心，EXAFS的表征同时表明由于Cu的添加而产生的Ru=0能加快反应速率。作者在此基础上提出反应机理，认为Ru在反应过程中形成醇化物，再经过β消除反应生成相应的醛或酮。     

Decomposition Characteristics of an Artificial Biogas in a Low‐Pressure DC Glow Discharge

The decomposition characteristics of an artificial biogas, which is a mixture of CH ₄, CO ₂, and H ₂ S, using a low‐pressure DC glow discharge have been investigated. It is found that H ₂, CO, C ₂ H ₂, H ₂ O, CS ₂, and COS are produced from the artificial biogas in the glow discharge. About 65% of the hydrogen atoms in CH ₄ are converted into H ₂ at an input energy of 800 J, at which CH ₄ is completely decomposed, and the decomposition characteristics of the artificial biogas are minimally dependent on the H ₂ S additive. Further, H ₂ S has a tendency to be decomposed earlier than the other components of the artificial biogas. When the glow discharge is generated in the artificial biogas with H ₂ S, some of the carbon atoms are found to deposit on the electrodes and the wall of the discharge chamber. © 2013 Wiley Periodicals, Inc. Electr Eng Jpn, 186(1): 26–33, 2014; Published online in Wiley Online Library ( wileyonlinelibrary.com ). DOI 10.1002/eej.22304     

NMR-Guided Repositioning of Non-Steroidal Anti-Inflammatory Drugs into Tight Junction Modulators

Bioavailability is a major bottleneck in the clinical application of medium molecular weight therapeutics, including protein and peptide drugs. Paracellular transport of these molecules is hampered by intercellular tight junction (TJ) complexes. Therefore, safe chemical regulators for TJ loosening are desired. Here, we showed a potential application of select non-steroidal anti-inflammatory drugs (NSAIDs) as TJ modulators. Based on our previous observation that diclofenac and flufenamic acid directly bound various PDZ domains with a broad specificity, we applied solution nuclear magnetic resonance techniques to examine the interaction of other NSAIDs and the first PDZ domain (PDZ1) of zonula occludens (ZO)-1, ZO-1(PDZ1). Inhibition of ZO-1(PDZ1) is expected to provide loosening of the epithelial barrier function because the domain plays a crucial role in maintaining TJ integrity. Accordingly, diclofenac and indomethacin were found to decrease the subcellular localization of claudin (CLD)-2 but not occludin and ZO-1 at the apicolateral intercellular compartment of Madin–Darby canine kidney (MDCK) II cells. These NSAIDs exhibited 125–155% improved paracellular efflux of fluorescein isothiocyanate insulin for the Caco-2 cell monolayer. We propose that these NSAIDs can be repurposed as drug absorption enhancers for peptide drugs.     

Cerebral Hyperperfusion after Revascularization Inhibits Development of Cerebral Ischemic Lesions Due to Artery-to-Artery Emboli during Carotid Exposure in Endarterectomy for Patients with Preoperative Cerebral Hemodynamic Insufficiency: Revisiting the “Impaired Clearance of Emboli” Concept

The purpose of the present study was to determine whether cerebral hyperperfusion after revascularization inhibits development of cerebral ischemic lesions due to artery-to-artery emboli during exposure of the carotid arteries in carotid endarterectomy (CEA). In patients undergoing CEA for internal carotid artery stenosis (≥70%), cerebral blood flow (CBF) was measured using single-photon emission computed tomography (SPECT) before and immediately after CEA. Microembolic signals (MES) were identified using transcranial Doppler during carotid exposure. Diffusion-weighted magnetic resonance imaging (DWI) was performed within 24 h after surgery. Of 32 patients with a combination of reduced cerebrovascular reactivity to acetazolamide on preoperative brain perfusion SPECT and MES during carotid exposure, 14 (44%) showed cerebral hyperperfusion (defined as postoperative CBF increase ≥100% compared with preoperative values), and 16 (50%) developed DWI-characterized postoperative cerebral ischemic lesions. Postoperative cerebral hyperperfusion was significantly associated with the absence of DWI-characterized postoperative cerebral ischemic lesions (95% confidence interval, 0.001–0.179; p = 0.0009). These data suggest that cerebral hyperperfusion after revascularization inhibits development of cerebral ischemic lesions due to artery-to-artery emboli during carotid exposure in CEA, supporting the “impaired clearance of emboli” concept. Blood pressure elevation following carotid declamping would be effective when embolism not accompanied by cerebral hyperperfusion occurs during CEA.     

Monitoring Technology for Gamma‐Aminobutyric acid Production in Polished Mochi Barley Grains using a Carbon Dioxide Sensor

Gamma‐aminobutyric acid (GABA) has many biological functions, including the inhibition of blood pressure increases and acceleration of growth hormone secretion. In this study, we discovered the utility of measuring the concentration of carbon dioxide (CO₂) dissolved in the reaction solution, for development of a real‐time and convenient technique to estimate GABA production. In addition to mochi barley bran, we examined the polished grains of three species: mochi barley (a variant of hulless barley), barley, and Japanese millet, all soaked in l ‐glutamic acid (l ‐Glu) solution at pH 4.5. We found a positive correlation between GABA and CO₂ concentrations, and the production of CO₂ was suppressed in the absence of l ‐Glu at pH 4.5. These results suggest that GABA content can be easily predicted by measuring the aqueous CO₂ content using a CO₂ sensor, during the process of GABA production in polished mochi barley grains and bran.     

Efficient characterization for protein crystals using confocal Raman spectroscopy

Confocal Raman spectroscopy was applied to the characterization of various states emerging in the screening of protein crystallization. Four main characterized states, namely single crystals, microcrystals, precipitates, and clear drops without solid materials, appear in a droplet for crystallization; the first three states should be critically distinguished and characterized because of the limitations of visual observation under an optical microscope. Using lysozyme and other proteins, crystallization was performed by the hanging drop vapor diffusion technique and was monitored through an automated confocal Raman system. Prior to the spectroscopic analysis, an optical microscope with a charge-coupled device (CCD) camera and associated image processing software were used to rapidly identify the XY locations to be measured spectroscopically by focusing the laser beam on a test sample. Instead of the current image analysis by optical microscopy, confocal Raman spectroscopy with a high spatial resolution was used to identify the state of protein crystallization. Such real-time Raman monitoring also distinguished real protein crystals from pseudo-protein crystals emerging in a crystallization droplet.     

Determination of potent antisense oligonucleotides in vitro by semiempirical rules

The selection of effective antisense target sites on a given mRNA molecule is a major problem in the detection of target mRNA in oligonucleotide arrays. In general, antisense oligodeoxynucleotides (asODNs) of about 10-20 nucleotides (nt) in length are used. However, the demand for predicting the sequence of potent asODNs much longer than those mentioned above has been increasing. Here, we prepared 40-nt asODNs directed against fluorescence-labeled green fluorescent protein (GFP) mRNA and quantified their hybridization efficiencies by fluorescence microscopy. We found that the hybridization efficiency depended on the TC content or the minimum free energy of the asODNs. On the basis of these findings, a semiempirical parameter called accessibility score was introduced to predict the potency of asODNs. The results of this study aided in the development of an effective two-step procedure for determining mRNA accessibility, namely, the computer-aided selection of asODN binding sites using an accessibility score followed by an experimental procedure for measuring the hybridization efficiencies between the selected asODNs and the target mRNA by fluorescence microscopy.     

Dimethylaminoethylated hydroxypropyl‐chitosan: Preparation and application as polymeric ligand to form Rh6 cluster complexes for the reduction of benzaldehyde and nitrobenzene

Hydroxypropyl chitosan and its dimethylaminoethylated derivative were prepared in different conditions. Experimental results indicated that the degree of substitution (DS) of hydroxypropyl chitosan was strongly related to the molar ratio of propylene oxide to the glucosamine unit of chitosan, the used solvent, the reaction temperature and the amount of sodium hydroxide. Moreover, the obtained hydroxypropyl chitosan could be effectively dimethylaminoethylated by the reaction with dimethylaminoethyl chloride in the presence of NaH under DMAC solution. By the combination of dimethylaminoethylated hydroxypropyl chitosan and Rh₆(CO)₁₆, benzaldehyde and nitrobenzene could be converted into correspondingly reductive products in high yields under the WGSR condition. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 447–453, 2001     

Theoretical study on controllability of quantum state energy in an InGaAs/GaAs quantum dot buried in InGaAs

We theoretically studied the relationship between quantum energy states and structural parameters of an InGaAs/GaAs quantum dot (QD) buried in strained InGaAs, emitting at 1.1 to 1.4 em. The crystal distortion of the buried QD structure in three dimensions was computed based on the three-dimensional finite element method. Under the computed strain fields, the Schr?dinger equation was solved to obtain wavefunctions and eigenenergies. By calculating the dependence on structural parameters, we investigated the controllable range of the ground state energy and the energy separation between the ground state and the first excited state. We found that the energy separation exhibited a maximum value as a function of QD composition, enabling us to identify the composition of the QD structure. The effects of the burying layer composition and QD diameter were also investigated to expand the controllable range of the state energy. We also showed that the wavefunction symmetry was improved by burying the QD in the InGaAs layer. Our results will be useful in developing advanced devices for optical telecommunications and quantum information technology.