Acid-catalyzed reaction of pyrazolo[1,5-a]pyridines with aldehydes: Formation of bis(pyrazolo[1,5-a]pyrid-3-yl)methane

Reaction of pyrazolo[1,5-a]pyridines with aldehydes in the presence of trifluoroacetic acid gave bis[pyrazolo[1,5-a]pyrid-3-yl)methanes in high yields.     

Heat capacity measurements of MnxFe3−xO4

Heat capacities of Mn_xFe_3?xO₄ with the composition x = 1.0, 1.5, and 2.0 were measured from 200 to 740 K. λ-type heat capacity anomalies due to the ferri-paramagnetic transition were observed for all the compositions. The transition temperatures were 577, 471, and 385 K for the composition x = 1.0, 1.5 and 2.0, respectively, which are in good agreement with the results of magnetic measurements. The difference in heat capacities between the different samples was small except for the temperature range of the transition. The magnetic contribution to the observed heat capacity was obtained by assuming that the heat capacity can be expressed by the sum of the lattice heat capacity C_v (l), the dilation contribution C(d), and the magnetic contribution C(m). Entropy changes due to the transition were obtained from C(m) as 55.5, 50.7 and 49.2 J K^?1 mole^?1 for the composition x = 1.0, 1.5, and 2.0, respectively. The entropy changes were also calculated by assuming the randomization of unpaired electron spins on each ion, but they were from 6 to 10 J K^?1 mole^?1 smaller than the observed ones. The difference between the experimental and the calculated values is roughly explained by taking into account the cation exchange reaction between the tetrahedral and the octahedral sites in the spinel structure.     

Arg-72 of pharaonis phoborhodopsin (sensory rhodopsin II) is important for the maintenance of the protein structure in the solubilized states

In bacteriorhodopsin (bR), Arg-82bR has been proven to be a very important residue for functional role of this light-driven proton pump. The arginine residue at this position is a super-conserved residue among archaeal rhodopsins. pharaonis phoborhodopsin (ppR; or called as "pharaonis sensory rhodopsin II") has its absorption maximum at 498 nm and acts as a sensor in the membrane of Natronobacterium pharaonis, mediating the negative phototaxis from the light of wavelength shorter than 520 nm. To investigate the role of the arginine residue (Arg-72ppR) of ppR corresponding to Arg-82bR, mutants whose Arg-72ppR was replaced by alanine (R72A), lysine (R72K), glutamine (R72Q) and serine (R72S) were prepared. These mutants were unstable in low concentrations of NaCl and lost their color gradually when the proteins were solubilized with 0.1% n-dodecyl-beta-D-maltoside. The order of instability was R72S > R72A > R72K > R72Q > the wild type. The rates of denaturation were reduced in a solution of high concentrations of monovalent anions.     

Ultra-slow Relaxation Dynamics in Triglycine Sulfate and D-Sorbitol Studied by Time-resolved Spectroscopy

The ultra-slow modes with a relaxation time much longer than 1 ns are discovered by a time-resolved spectroscopy in uniaxial ferroelectric (NH₂CH₂COOH)₃H₂SO₄ (TGS) and in glass-former HOCH₂(CHOH)₄CH₂OH (D-sorbitol). A mode discovered in TGS is a thermal relaxational mode and is proved to be the physical origin of the central peak found by Brillouin scattering. Two modes are discovered in D-sorbitol. One is a thermal relaxational mode. The other is a mode characterized by the Kohlraush-Williams-Watts function with a relaxation time _R. A remarkable result is that _R indicates a critical behavior not at the liquid-glass transition temperature T_g =–7°C but at the ergodic to nonergodic transition temperature T_c=33°C.This revised version was published online in November 2005 with corrections to the Cover Date.     

Diarylurea-linked zinc porphyrin dimer as a dual-mode artificial receptor: supramolecular control of complexation-facilitated photoinduced electron transfer

A novel porphyrinic receptor 1 in which two zinc porphyrins are bridged by two diarylurea linkers was developed for recognition of a viologen derivative (hexyl viologen, HV). The electronic absorption spectra as well as the 1H NMR experiments revealed that the HV molecule was bound to the cleft in 1 mainly through carbonyl dipole-charge interactions to afford a 1:1 complex. From the steady-state fluorescence spectroscopic study, the photoinduced electron transfer (PET) from 1 to HV was extremely facilitated by the receptor-substrate complexation. The receptor 1 also formed a 1:1 complex with 1,4-diazabicyclo[2.2.2]octane (DABCO) through two Zn-N coordination interactions, and, using DABCO as an inhibitor, we suppressed the PET reaction via the substrate exchange.     

Broad spectrum and mode of action of an antibiotic produced byScytonema sp. TISTR 8208 in a seaweed-type bioreactor

A photobioreactor was constructed using anchored polyurethane foam strips (1 x 1 x 40 cm) fixed onto a stainless-steel ring to prevent flotation, as a biomass support material (BSM). This type of reactor was named a seaweed-type bioreactor. A filamentous cyanobacterium, Scytonema sp. TISTR 8208, which produces a novel cyclic dodecapeptide antibiotic, was immobilized in seaweed-type photobioreactor and cultivated with air containing 5% CO₂ sparged at a gas flow rate of 250 mL/min under illumination at a light intensity of 200 μmol photon m^-2s^-1. The antibiotic produced in the seaweed-type photobioreactor was purified by HPLC and examined regarding its spectrum and mode of action. The antibiotic effectively inhibited the growth of Gram-positive bacteria, pathogenic yeasts, and filamentous fungi, but it had only a weak effect on Gram-negative bacteria. Scanning electron micrograph analysis showed that the most characteristic change was swelling of the cells after exposure to the antibiotic. The antibiotic seems to alter the conformation of the microbial cell membrane, thereby changing its permeability, leading to osmotic shock.     

Highly accurate and precise multielement determination of environmental samples by means of photon activation using the internal standard method

In order to examine effective applications of the newly developed internal standard method, determinations of Cr, Co, Ni, Zn, As, Rb, Sr, Y, Zr, Nb, Cs, Ce and Pb in three environmental materials, such as pond, lake and estuarine sediments, have been tried by means of photon activation. In these examinations, some major constituent elements in the above sediments were properly used as excellent and effective internal standards. In consequence, it was confirmed that highly accurate and precise determinations of the above 13 elements were achieved easily and favourably.     

1,6-dihydro-3(2H)-pyridinones as synthetic intermediates. Total synthesis of (±)-tecomanine

The first and stereoselective total synthesis of (±)-tecomanine ($\text{1}$) has been achieved from ethyl 1,6-dihydro-3(2H)-pyridinone-1-carboxylate ($\text{2}$) as a synthon.     

meso-Diazacorrphycenes: Neighboring Effect of Two Nitrogen Atoms

The neighboring effect of two adjacent heteroatoms influences the structures and properties of heterocyclic compounds. Herein, we demonstrated that the introduction of two adjacent sp² nitrogen atoms into a porphyrinic skeleton significantly enhanced its Brønsted basicity due to the repulsive interaction between two lone pairs on the nitrogen atoms. Palladium- and copper-templated ring closure of dichlorobis(dipyrrin) with hydrazine hydrate provided meso-diazacorrphycene palladium and copper complexes in good yields. The structural, magnetic, and electrochemical properties of the diazacorrphycene complexes were investigated experimentally and theoretically to elucidate the effect of the meso-nitrogen atoms.