Formation of highly ordered porphyrin adlayers induced by electrochemical potential modulation

Molecular self-assembly of porphyrin derivatives formed with intermolecular hydrogen bonding on the surface of Au(111) electrode in acidic solution can be controlled by varying the number of peripheral carboxy groups and the applied electrochemical potential.     

Synthesis,crystal structure,and FET characteristics of thieno[2,3-b]thiophene-based bent-thienoacenes

Two novel bent-shaped thienoacenes, naphtho[2,3-b]naphtho[2′,3′:4,5]thieno[3,2-d]thiophene (bent-DNTT) and anthra[2,3-b]anthra[2′,3′:4,5]thieno[3,2-d]thiophene (bent-DATT) were synthesized from thieno[2,3-b]thiophene and their corresponding aromatic anhydrides by three steps: Friedel–Crafts acylation, acid-promoted cyclization, and reductive aromatization. The structural curvature improved the solubility of these thienoacenes in organic solvents. The bent-DNTT based FET device was fabricated by the spin-coating method. The device exhibited p-type characteristics with a mobility of 5.1 × 10^?5 cm² V^?1 s^?1. Its thin-film structure was fully characterized as an edge-on orientation with large intermolecular orbital coupling.     

Electrogenerated chemiluminescence with solvated electrons in hexamethylphosphoroamide (HMPA)

The electrogenerated chemiluminescence of N-toluenesulfonyl carbazole, 9-chlorofluorene derivatives and N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD) with solvated electrons in HMPA are discussed. The fairly bright emissions occurred simultaneously when solvated electrons were generated electrochemically. In the case of N-toluenesulfonyl carbazole and 9-chlorofluorene derivatives, the respective carbanions formed by “dissociative electron transfer reactions” are the fluorescents. The singlet state of TMPD seems to be directly formed by the electron transfer reactions between radical cations of TMPD and solvated electrons.     

The Effects of Cyclodextrins on Autoinducer Activities of Quorum Sensing in Pseudomonas aeruginosa

Inclusion complex formation between cyclodextrin and autoinducer of gram negative bacteria in aqueous solution was investigated by 1D ¹H-NMR and ROESY spectra. An inhibitioneffect was observed on autoinducer activities of quorum sensing in Pseudomonas aeruginosa by adding cyclodextrins to the bacterial culture medium.     

Scanning tunneling microscopy of sulfur and benzenethiol chemisorbed on Ru(0001) in 0.1 M HClO4

In situ scanning tunneling microscopy (STM) combined with linear sweep voltammetry was used to examine spatial structures of sulfur adatoms (SA) and benzenethiol (BT) molecules adsorbed on an ordered Ru(0001) electrode in 0.1 M HClO4. The Ru(0001) surface, prepared by mechanical polishing and electrochemical reduction at -1.5 V (vs RHE) in 0.1 M HClO4, contained atomically flat terraces with an average width of 20 nm. Cyclic voltammograms obtained with an as-prepared Ru(0001) electrode in 0.1 M HClO4 showed characteristics nearly identical to those of Ru(0001) treated in high vacuum. High-quality STM images were obtained for SA and BT to determine their spatial structures as a function of potential. The structure of the SA adlayer changed from (2 x mean square root of 3)rect to domain walls to (mean square root of 7 x mean square root of 7)R19.1 degrees and then to disordered as the potential was scanned from 0.3 to 0.6 V. In contrast, molecules of BT were arranged in (2 x mean square root of 3)rect between 0.1 and 0.4 V, while they were disordered at all other potentials. Adsorption of BT molecules was predominantly through the sulfur headgroup. Sulfur adatoms and adsorbed BT molecules were stable against anodic polarization up to 1.0 V (vs RHE). These two species were adsorbed so strongly that their desorption did not occur even at the onset potential for the reduction of water in 0.1 M KOH.     

Integrated-optic variable delay line and its application to a low-coherence reflectometer

We propose a large-scale variable delay line based on planar light-wave circuit technology and its application as a reference arm in an optical low-coherence reflectometer. This variable delay line is composed of 16 asymmetrical delay arm pairs sandwiched between 2 optical switches, which select the path for a needed delay. This configuration enables us to eliminate the need for a moving part in the reflectometer. We can scan the reference arm over a length of 262.1 mm with a step of less than 1.0 microm in air and achieve reflectometer sensitivity of about -47 dB.     

Liposomes possess drastic capabilities for topological transformation

Morphological and topological changes of biological membranes play essential roles in cellular activities. It has been thought that these transformations are made possible through interactions with proteins. However, direct observation of giant liposomes by optical dark-field microscopy reveals that the lipid bilayer itself possesses the ability to undergo topological transformation.     

Optical orthogonal frequency division multiplexing demultiplexer using slab star coupler-based optical discrete Fourier transform circuit

We demonstrate an optical orthogonal frequency division multiplexing (OFDM) demultiplexer with an optical discrete Fourier transform circuit fabricated using silica planar lightwave circuit technology. This compact device can process an arbitrary number of subcarriers. The operation of a ten-channel device is demonstrated by demultiplexing a 100 Gbit/s (10 subcarrier × 10 Gbits/s) OFDM signal. We also discuss a main factor affecting characteristics degradation of the device.     

Instrumental Neutron Activation Analysis of Trace Elements in Organs and Tissues of Zinc Deficient Mice

Eleven elements in ten organs and tissues of mice fed with Zn-deficient diet (Zn-def. mice) and those fed with control diet (control mice) were determined by INAA. Zinc concentrations in the organs of Zn-def. mice were not distinctly lower than those of control mice except for bone and pancreas, as similar to the predecessors' reported results. However, the Co content increased significantly in all the organs and tissues of Zn-def. mice compared with control mice. The organs and tissues observed were histologicaly normal and no typical symptoms of Zn deficiency disease were recognised. The results suggest that the change of Co-concentration may be regarded as a mark of the prestage for a Zn deficiency disease.     

Electrochemical control of the structure of two-dimensional supramolecular organization consisting of phthalocyanine and porphyrin on a gold single-crystal surface

Two-component adlayers consisting of cobalt(II) phthalocyanine (CoPc) and a metalloporphyrin such as 5,10,15,20-tetraphenyl-21H,23H-porphine copper(II) (CuTPP), 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine copper(II) (CuOEP), or 5,10,15,20-tetraphenyl-21H,23H-porphine cobalt(II) (CoTPP) were prepared by immersing either an Au(111) or Au(100) substrate in a benzene solution containing those molecules. The mixed adlayers thus prepared were investigated in 0.1 M HClO4 by cyclic voltammetry (CV) and in situ scanning tunneling microscopy (STM). The composition of the mixed adlayer consisting of CoPc and CuTPP molecules was found to vary with immersion time. CoPc molecules displaced CuTPP molecules during the modification process with increasing immersion time, and the CuTPP molecules were completely displaced by CoPc molecules in the mixed solution after a prolonged modification time, during which the underlying Au(100) substrate underwent phase transition from the reconstructed (hex) lattice to the unreconstructed (1 x 1) lattice. The two-component adlayer of CoPc and CuTPP was found to form a supramolecular adlayer with the constituent molecules arranged alternately on Au(100)-(hex). The striped structure was stable on Au(100)-(hex) at or near the open circuit potential (OCP), whereas the mixed adlayer was disordered on Au(100)-(1 x 1) at potentials more positive than OCP, where the phase transition of the arrangement of underlying Au atoms (i.e., the lifting of reconstruction) was induced electrochemically. A similar two-component supramolecular adlayer consisting of CoPc and CuTPP was formed on Au(111). A highly ordered, compositionally disordered adlayer of CoTPP and CuTPP was formed on Au(100)-(hex), suggesting that the adlayer structure is independent of the coordinated central metal ion for the formation of supramolecular nanostructures composed of those molecules. A supramolecular organization of CoPc and CuOEP was also found on Au(111). The surface mobility and the molecular reorganization of CoPc and CuOEP on Au(111) were tuned by modulation of the electrode potential. It is concluded that molecular assemblies of the two-component structure consisting of phthalocyanine and porphyrin were controlled not only by the crystallographic orientation of Au but also by the modulation of electrochemical potential.