Controlled chain polymerisation and chemical soldering for single-molecule electronics

Single functional molecules offer great potential for the development of novel nanoelectronic devices with capabilities beyond today's silicon-based devices. To realise single-molecule electronics, the development of a viable method for connecting functional molecules to each other using single conductive polymer chains is required. The method of initiating chain polymerisation using the tip of a scanning tunnelling microscope (STM) is very useful for fabricating single conductive polymer chains at designated positions and thereby wiring single molecules. In this feature article, developments in the controlled chain polymerisation of diacetylene compounds and the properties of polydiacetylene chains are summarised. Recent studies of "chemical soldering", a technique enabling the covalent connection of single polydiacetylene chains to single functional molecules, are also introduced. This represents a key step in advancing the development of single-molecule electronics.     

Rates for intramolecular excimer formation of poly(α-methylstyrene) measured by using picosecond pulse radiolysis

Summary The rate constants for intramolecular excimer formation, k_DM, of poly(α-methylstyrene) with different molecular weight were determined by using picosecond pulse radiolysis. Values of k_DM for poly(α-methylstyrene) are a little smaller than those for polystyrene with nearly same molecular weight. It appears to be mainly due to steric hindrance by methyl substituent of main chain.     

The effect of the framework structure on the chemical properties of the vanadium oxide species incorporated within zeolites

V-silicalite catalysts (VS-1 and VS-2) prepared by hydrothermal synthesis have been studied by ESR, XAFS (XANES and EXAFS) and photoluminescence spectroscopy. The in situ characterization of these V-silicalites shows that vanadium is present within the zeolitic framework as a highly dispersed tetrahedrally coordinated V-oxides, VO₄ unit, having a short V=O bond length. Photoluminescence spectroscopy in static and dynamic mode, as well as XAFS studies allow to detect in the V-silicalites different V species than that present in V-HMS or V/SiO₂, in terms of V=O bond length, vibrational energy, bond angle and lifetime of the excited triplet state. It is suggested that the combined contribution of the neighboring Si---OH group attached to the VO₄ unit and the zeolitic rigid framework structure of V-silicalites cause a more significant and pronounced effect on the chemical properties of the VO₄ unit than the flexible structure of V-HMS or V/SiO₂. Moreover, the dynamic quenching of the phosphorescence by the addition of reactant molecules such as NO or propane indicates that the V species in the excited triplet state can be expected to be the active sites for the photocatalytic reactions.     

Drying of Sewage Sludge During Composting in an Updraft Dryer with the Concept of Using Self-Energy Generated Within the System

An innovative technology for sewage treatment systems is proposed. A mixture of sewage sludge and char particle is subjected to drying in the progress of composting in an updraft column. Exothermic heat generated during composting is utilized for energy of sludge drying. The char particle in the mixture contributes to enhancement of composting and drying rate. This study presents drying and composting behaviors of sludge to examine the effect of char addition. A fundamental drying experiment was carried out by hot-air heating of the sample in a small vessel. The drying characteristic curve for a mixture of sludge and char was greater than the sample of only sludge over a whole period if the drying rates were compared with the same moisture content. The drying behavior could be analyzed with a reasonable agreement by the water front receding model. The enhancement effect of drying and composting of sludge by char addition was confirmed by examination using a pilot scale of the updraft column whose volume was 50 m³. Sludge with 400% dry base (80% wet base) in moisture content could be dried successfully to lower moisture content than 67% dry base (40% wet base) only by exothermic heat during composting without supplying any auxiliary energy from the outside, and the treatment time was reduced by mixing char in sludge. The behavior was analyzed with a satisfactory agreement by a theoretical model employing moisture diffusion parameters determined from the drying characteristic curve.     

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.     

Hydrophobic Tagged Dihydrofolate Reductase for Creating Misfolded Glycoprotein Mimetics

In the endoplasmic reticulum (ER), nascent glycoproteins that have not acquired the native conformation are either repaired or sorted for degradation by specific quality‐control systems composed by various proteins. Among them, UDP‐glucose:glycoprotein glucosyltransferase (UGGT) serves as a folding sensor in the ER. However, the molecular mechanism of its recognition remains obscure. This study used pseudo‐misfolded glycoproteins, comprising a modified dihydrofolate reductase with artificial pyrene–cysteine moiety on the protein surface (pDHFR) and Man₉GlcNAc₂‐methotrexate (M9‐MTX). All five M9‐MTX/pDHFR complexes, with a pyrene group at different positions, were found to be good substrates of UGGT, irrespective of the site of pyrene modification. These results suggest UGGT's mode of substrate recognition is fuzzy, thus allowing various glycoproteins to be accommodated in the folding cycle.     

Comparison of activities in selective catalytic reduction of NOx by C3H8 over Co/MFI, Fe/MFI, and H/MFI zeolite catalysts

The Co/MFI(SiO₂/Al₂O₃ = 30) were prepared by a precipitation method with NaOCl in alkali solutions exhibited high activities to N₂ at 250 °C for the selective catalytic reduction (SCR) of NO_x. These catalysts showed two UV–vis bands at 700 and 400 nm, indicating the presence of octahedral Co(III) as well as tetrahedral Co(II). The high SCR activity over such Co(III, II)/MFI(30) seems to come from Co(III)---O moieties. The Co(II)MFI(30) catalysts prepared from Co(II)Cl₂ exhibited low SCR activities due to the presence of tetrahedral Co(II) ions in MFI. Less CO formation occurred over Co/MFI catalysts. The Fe/MFI(30) catalyst exhibited high activity due to the presence of some Fe---O species in MFI but more amount of CO were produced during SCR. H/MFI(30) catalyst exhibited a good SCR activity. However, more amount of carbonaceous deposits were produced on it. The correlation between acid concentration and SCR activity was discussed over H/MFIs.     

Investigation on twisting distortion of thin plate stiffened structure under welding

The welding distortion of thin plate was selected as research subject, which causes loss of dimensional control, structural integrity and increases fabrication costs for straightening. To study the characteristic of the welding distortion on thin plate structures, experiments were conducted. The test model was a thin plate stiffened structure and a large twisting distortion was observed. The welding distortion of the same structure was analyzed as a large deformation problem using a thermal elastic plastic FEM and an elastic FEM based on the concept of inherent deformation. The computed results by both methods showed the twisting distortion which is a typical buckling type deformation and the magnitude of this distortion agreed well with the experimental measurement.     

The effect of the hydrothermal treatment with aqueous NaOH solution on the photocatalytic and photoelectrochemical properties of visible light-responsive TiO2 thin films

The effect of the hydrothermal treatment with aqueous NaOH solution on the photoelectrochemical and photocatalytic properties of visible light-responsive TiO₂ thin films prepared on Ti foil substrate (Vis-TiO₂/Ti) by a radio-frequency magnetron sputtering (RF-MS) deposition method has been investigated. The hydrothermally treated Vis-TiO₂/Ti electrodes exhibited a significant increase in their photocurrent under UV and visible light irradiation as compared to untreated Vis-TiO₂/Ti electrode. SEM investigations revealed that the surface morphology of Vis-TiO₂/Ti are drastically changed from the assembly of the TiO₂ crystallites to the stacking of nanowires with diameters of 30–50 nm with increasing hydrothermal treatment time (3–24 h), accompanying the increase in their surface area. The separate evolution of H₂ and O₂ from water under solar light irradiation was successfully achieved using the Vis-TiO₂/Ti/Pt which is hydrothermally treated for 5 h, while the H₂ evolution ratio was 15 μmol h⁻¹ in the early initial stage, corresponding to a solar energy conversion efficiency of 0.23%.