Synthesis of directly linked zinc(II) porphyrin-imide dyads and energy gap dependence of intramolecular electron transfer reactions

A series of zinc(II) porphyrin-imide dyads (ZP-Im), in which an electron donating ZP moiety is directly connected to an electron accepting imide moiety in the meso position, have been prepared for the examination of energy gap dependence of intramolecular electron transfer reactions with large electronic coupling. The nearly perpendicular conformation of the imide moiety towards the porphyrin plane has been revealed by Xray crystal structures. The energy gap for charge separation, 1ZP* - Im --> ZP+ - Im-, is varied by changing the electron accepting imide moiety to cover a range of about 0.8 eV in DMF. Definitive evidence for electron transfer has been obtained in three solvents (toluene, THF, and DMF) through picosecond-femtosecond transient absorption studies, which have allowed us to determine the rates of photoinduced charge separation, 1ZP* - Im --> ZP+ - Im-, and subsequent thermal charge recombination ZP+ - Im- --> ZP - Im. The free-energy gap dependence (energy gap law) has been probed from the normal to the nearly top region for the charge separation rate alone, and only the inverted region for the charge recombination rate. Although both of the energy gap dependencies can be approximately reproduced by means of the simplified semiclassical equation, when we take into consideration the effect of the high frequency vibrations replaced by one mode of averaged frequency, many features, including the effects of solvent polarity and the electron tunneling matrix element on the energy gap law, differ considerably from those of the previously studied porphyrin-quinone systems, which have weaker interchromophore electronic interactions.     

Tetra‐n‐butyl­ammonium tetrakis(penta­fluoro­benzenethiol­ato‐κS)­aurate(III)

The title compound, (C₁₆H₃₆N)[Au(C₆F₅S)₄], is the first example of a structurally characterized gold(III) complex with monodentate benzene­thiol­ate ligands. The Au atom lies on a fourfold axis and the AuS₄ group has square‐planar geometry. The anion shows a two‐dimensional linkage through π–π and C—F⋯π intermolecular interactions.     

Stereospecific synthesis of new 2,3,4,5-piperidinetetracarboxylic acids and 2,3,5-piperidinetricarboxylic acids

Diels-Alder adducts of 1,2-dihydropyridine with maleic and acrylic acid derivatives were stereospecifically converted by way of RuO₄ oxidation into new r-2,c-3,c-4,c-5-piperidinetetracarboxylic acid, r-2,t-3,t-4,c-5-piperidinetetracarboxylic acid, r-2,c-3,c-5-piperidinetricarboxylic acid, and r-2,t-3,c-5-piperidinetricarboxylic acid.     

N-long-chain monoacylated derivatives of 2,6-diaminopyridine with antiviral activity

N-Monoacyl-2,6-diaminopyridines (2a-c) and N,N'-diacyl-2,6-diaminopyridines (3a-c) were synthesized from 2,6-diaminopyridine by acylation with the corresponding acyl halide or by dehydration with the corresponding carboxylic acid using 1,3-dicyclohexylcarbodiimide (DCC). The antiviral activities of N-monoacyl- and N,N'-diacyl-2,6-diaminopyridines (2a-c and 3a-c) were estimated using plaque reduction assay with HSV-1. All N-monoacyl derivatives (2a-c) showed significant anti-herpes simplex virus (HSV)-1 activity (EC(50) = 15.3-18.5 microg/ml). The CC(50) values of 2a-c measured using Vero cells ranged at 37.5-50.0 microg/ml. These compounds showed no significant antibacterial activities with Escherichia coli or Staphylococcus aureus even at a concentration of 1 mg/ml. The N,N'-diacyl derivatives (3a-c) showed no significant anti-HSV-1 activity.     

Array of aromatic amino acid side chains located near the chromophore of photoactive yellow protein

The role of the array of aromatic amino acid side chains located close to the chromophore binding loop of photoactive yellow protein (PYP) was studied using the alanine-substitution mutagenesis. Phe92, Tyr94, Phe96 and Tyr98 were replaced with alanine (F92A, Y94A, F96A and Y98A, respectively), then these mutants were characterized by UV-visible absorption spectra, circular dichroism (CD) spectra, thermal stability and photocycle kinetics. Absorption maxima of F92A, Y94A, F96A and Y98A were 444, 442, 439 and 447 nm, respectively, different to wild type (WT) at 446 nm. Far-UV CD spectra of mutants other than F92A were different from WT, indicating that Tyr94, Phe96 and Tyr98 maintain the native secondary structure of PYP. Mid-point temperatures of thermal denaturation of F92A, Y94A and F96A, estimated by the CD signal at 222 nm, were 5-10 degrees C lower than WT. Time constants of the photocycle estimated by flash-induced absorbance change were 0.36 s for WT and 1.4 s for Y98A, however, 100, 30 and 3000 times slower than WT for F92A, Y94A and F96A, respectively. Tyr98 is located in the loop region, whereas Phe92, Tyr94 and Phe96 are incorporated in the beta4 strand, showing that aromatic amino acid residues in the beta-sheet regulate the absorption spectrum, thermal stability and photocycle of PYP. Aromatic rings of Phe92, Tyr94 and Phe96 lie nearly perpendicular to the aromatic ring of Phe75 or chromophore. Possible weak hydrogen bonds between the aromatic ring hydrogen and pi-electrons of these residues are discussed.     

Proteomic LC-MS systems using nanoscale liquid chromatography with tandem mass spectrometry

Current nano-scale liquid chromatography-tandem mass spectrometry (nanoLC-MS/MS) approaches in proteome research are reviewed from an analytical perspective. For comprehensive analysis of cellular proteins, analytical methods with higher resolution, sensitivity, and wider dynamic range are required. Miniaturized LC coupled with tandem mass spectrometry is currently one of the most versatile techniques. In this review, the current status of nanoLC-MS/MS systems as well as data management systems is addressed. In addition, the future prospects for complete proteomics are discussed.     

Effective, fast, and low temperature encapsulation of fullerene derivatives in single wall carbon nanotubes

High filling of single wall nanotubes (SWCNTs) with the typical exohedrally functionalized fullerene derivative of C₆₀N-methyl-3,4-fulleropyrrolidine C₆₀-C₃NH₇ is reported at the temperature of refluxing hexane. The new peapod material is characterized by STM (scanning tunneling microscopy), TEM (transmission electron microscopy) and Raman spectroscopy. Atomically resolved STM scans on SWCNT show no excessive defects or sidewall functionalization as a result of this treatment. The radial breathing mode (RBM) mode of SWCNT at 165 cm⁻¹ becomes weaker and shifted to 169 cm⁻¹ indicating filled nanotubes. TEM studies show bundles of SWCNT are highly filled with derivative C₆₀-C₃NH₇ and form the (C₆₀-C₃NH₇)_n peapods. Individual pyrrolidine-type functional groups attached to the fullerene cages are unambiguously visualized by a lower-dose observation.     

Measurement Accuracy in Phase-Shifting Point Diffraction Interferometer with Two Optical Fibers

A phase-shifting point diffraction interferometer (PS/PDI) with point sources of two single mode optical fibers has been developed, which will be appropriate for the surface figure measurement of large aperture optics on a sub-nanometer scale. To reduce the measurement error factors, a fiber optic plate (FOP) is used as a projection plane for interference pattern. Errors caused by imperfection of optical alignment, such as position of point sources and tilt of FOP, are minimized by analyzing the measured phase data with an original method. Measurement accuracy in the PS/ PDI is estimated with the interference pattern produced by the two optical fiber sources. If inhomogeneity of the FOP and a systematic error of the PS/PDI are eliminated, the measurement accuracy of the present system is estimated to be less than 4nm P-V and 0.7nm rms, respectively, at a measurement wavelength of 632.8 nm.