A novel mediator-polymer-modified anode for microbial fuel cells

A high-performance anode system based on a combination of mediator-polymer-modified graphite felt and bacteria capable of reducing extracellular materials shows significant potential for practical use in microbial fuel cells (MFCs).     

Stereoselective synthesis of benzyl-protected β-galactosides by propionitrile-mediated glycosylation

β-Selective galactosylation was studied using a series of 2-O-benzylated phenyl 1-thio-galactosides and glycosyl acceptors in propionitrile with BSP-TTBP-Tf₂O. The glycosylation enabled us to synthesize useful precursors of N-acetyllactosamine and core 1 O-glycoserine derivatives in a highly convergent manner.     

Electronic polarizability and Judd-Ofelt parameters of Nd3+ and Er3+ ions in transparent crystallized glasses with nonlinear optical Ba2 TiSi2O8 nanocrystals

Transparent crystallized glasses consisting of nonlinear optical Ba(2)TiSi(2)O(8) nanocrystals are prepared in Eu(2)O(3)-, Nd(2)O(3)-, and Er(2)O(3)-doped 40BaO-20TiO(2)-40SiO(2) glasses by a conventional heat treatment method in order to clarify the optical properties of rare-earth (RE) ions in nanocrystals. The electronic polarizabilities of crystallized glasses are evaluated from the values of density and refractive index, and are found to decrease due to nanocrystallization, which indicates that the chemical bonding state in the crystallized glasses is more covalent compared to the precursor glasses. It is proposed from x-ray diffraction analyses and photoluminescence spectra of Eu(3+) ions that RE ions such as Nd(3+) and Eu(3+) are incorporated into Ba(2)TiSi(2)O(8) nanocrystals. The Judd-Ofelt parameters, Omega(t) (t=2, 4, and 6), of Nd(3+) and Er(3+) ions are evaluated from optical absorption spectra. It is observed that the Omega(2) parameter of Nd(3+) and Er(3+) increases largely due to nanocrystallization, suggesting that the site symmetry of Nd(3+) and Er(3+) ions in nanocrystallized glasses is largely distorted due to their incorporations into the Ba(2+) sites in Ba(2)TiSi(2)O(8) nanocrystals. The change in the Omega(4) and Omega(6) parameters due to nanocrystallization is small. It is proposed that nonlinear optical Ba(2)TiSi(2)O(8) nanocrystals including RE ions would have a high potential as active optical materials.     

Separation of nanocarbons by molecular recognition

This review article surveys the author’s work during the last ten years. The research works have been carried out in the interdisciplinary fields of supramolecular, synthetic organic and materials chemistry. This review consists of the following 5 topics; (1) novel synthetic methodology for constructing benzyl ether-linked oxacyclophanes and oxacalixarenes by reductive coupling reactions, (2) preferential precipitation of C₇₀ over C₆₀ with p-halohomooxacalix[3]arenes prepared by the above reductive coupling reactions, (3) highly practical purification of fullerenes by filtration through activated carbon thin layer, (4) host-guest chemistry of C₆₀ and C₇₀ with porphyrin monomers and dimers in solution, and (5) optical resolution of carbon nanotubes through preferential complexation with chiral diporphyrin nanotweezers. New terminology is also proposed in the definition of the structures and stereochemistry of carbon nanotubes.     

Protein nanotubes comprised of an alternate layer-by-layer assembly using a polycation as an electrostatic glue

We present the synthesis and structure of various protein nanotubes comprised of an alternate layer-by-layer (LbL) assembly using a polycation as an electrostatic glue. The nanotubes were fabricated by sequential LbL depositions of positively charged polycations and negatively charged proteins into a porous polycarbonate (PC) membrane, followed by release of the cylindrical core by quick dissolution of the template with CH(2)Cl(2). This procedure provides a variety of protein nanotubes without interlayer cross-linking. The three-cycle depositions of poly-L-arginine (PLA) and human serum albumin (HSA, M(w)=66.5 kDa) into the porous PC template (pore diameter, D(p)=400 nm) yielded well-defined (PLA/HSA)(3) nanotubes with an outer diameter of 419+/-29 nm and a wall thickness of 46+/-8 nm, revealed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. The outer diameter of the tubules can be controlled by the pore size of the template (200-800 nm), whereas the wall thickness is always constant, independent of the D(p) value. The (PEI/HSA)(3) (PEI: polyethylenimine) nanotubes showed a slightly thin wall of 39+/-5 nm. CD spectra of the multilayered (PEI/HSA)(n) film on a flat quartz plate suggested that the secondary structure of HSA between the polycations was almost the same as that in aqueous solution. The three-cycle LbL depositions of PLA and ferritin (M(w)=460 kDa) or myoglobin (Mb, M(w)=1.7 kDa) into the porous PC membrane also gave cylindrical hollow structures. The wall thickness of the (PLA/ferritin)(3) and (PLA/Mb)(3) nanotubes were 55+/-5 nm and 31+/-4 nm; it depends on the globular size of the protein (ferritin>HSA>Mb). The individual ferritin molecule was clearly seen in the tubular walls by SEM and TEM measurements.     

Quantum dot FRET biosensors that respond to pH, to proteolytic or nucleolytic cleavage, to DNA synthesis, or to a multiplexing combination

Fluorescent acceptors have been immobilized on nanoparticulate quantum dots (QDs), which serve in turn as their FRET donors. The broad excitation and narrow emission bands of QDs mark them as having excellent potential as donors for FRET and, in principle, differently colored QDs could be excited simultaneously. The present work describes the preparation and operation of FRET-based QD bioprobes individually able to detect the actions of protease, deoxyribonuclease, DNA polymerase, or changes in pH. In addition, two such QD-mounted biosensors were excited at a single wavelength, and shown to operate simultaneously and independently of each other in the same sample solution, allowing multiplex detection of the action of a protease, trypsin, in the presence of deoxyribonuclease.     

Several explicit formulae of Cauchy polynomials in terms of {r}-Stirling numbers

The integer values of Cauchy polynomials are expressed in terms of \({r}\)-Stirling numbers of the first kind. Several relations between the integral values of Bernoulli polynomials and those of Cauchy polynomials are obtained in terms of \({r}\)-Stirling numbers of both kinds. Also, we find a relation between the Cauchy polynomials and hyperharmonic numbers.     

Spectral and theoretical studies on effective and selective non-covalent interaction between tetrahexylporphyrins and fullerenes

The host-guest interaction of zinc(II) 5,10,15,20-tetrahexylporphyrin (Zn-THP) and its free base (H2-THP) with fullerenes (C60 and C70) has been studied in toluene medium. Binding constants (K) for H2- and Zn-THP complexes of fullerenes were determined by UV-vis, fluorescence and NMR spectroscopic techniques. Large K values of C70/THP complexes (KC70 ) were obtained in the range of 1.4-2.5 x 10(4)M(-1), while those of C60/THP complexes (KC60) were smaller (1.0-3.2 x10(3)M(-1)). These results show that the KC70 is about 10 times as large as KC60 in both THPs (KC70/KC60 = 10). Enthalpies of formation (DeltaHf degrees) for various fullerene/THP complexes were estimated by ab initio calculations; DeltaHf degrees for C60/H2-THP, C70/H2-THP, C60/Zn-THP and C70/Zn-THP complexes are 5.82, 2.80, 2.31 and 1.54 kcal mol(-1), respectively. The trends in DeltaHf degrees support the experimental results of selective complexation of THPs towards C70 over C60 and fullerenes towards Zn-THP over H2-THP.     

Dependence of the photoelectrochemical performance of sensitised ZnO on the crystalline orientation in electrodeposited ZnO thin films

The influence of the crystal orientation in porous crystalline films of ZnO electrodeposited on the photoelectrochemical characteristics of the films is studied. For differently oriented ZnO thin films following removal of the respective structure-directing agent (SDA) and adsorption of a sensitiser, time-resolved photocurrent measurements, intensity modulated photocurrent spectroscopy (IMPS), intensity modulated photovoltage spectroscopy (IMVS) and current-voltage curves were measured in acetonitrile-based electrolytes containing I(3)(-)/I(-) as the redox electrolyte. The crystal orientation has a significant influence on the charge transport across such films and hence is reflected in the observed electrode kinetics. Films originally grown in the presence of, e.g., Coumarin 343 as a SDA, showed a significantly faster response to illumination. Increased electron diffusion coefficients and diffusion lengths were calculated from the results of IMPS and IMVS, caused by a faster electron movement in the films. Implications of these findings on further improvements of sensitised ZnO films prepared by electrochemical deposition are discussed.