Synthesis of tetra-aza macrocycles with remarkably high efficiency

Tetra-aza macrocycles with 28- to 44-membered rings can be readily synthesized by reaction of dibromide and ditosyldiamide without use of a high dilution method. The reaction proceeded very smoothly with a 10 mM concentration in DMF, and gave the macrocycles in excellent yields (60–80%). Favorable effects of cesium ion on the cyclization have been observed.     

SOL-detectability of liver SPECT--analysis by SOL detection model

The purpose of this study is to evaluate the clinical efficacy of liver SPECT (single photon emission computed tomography). Eleven hospitals which are in or near Tokyo are participating in this study. Planar liver images and SPECT images of 134 cases which were retrospectively confirmed for its final diagnosis were collected. At the first study, the planar images (PS) were read by 13 nuclear medicine physicians. The second, the image reading by the combination of the planar images and the SPECT images (PS + SPECT) were performed. The confidence level of diagnosis for SOL (space occupying lesion) obtained by the image reading of PS and PS + SPECT has been analyzed by using the SOL detection model. The SOL detectability of PS + SPECT was higher than that of PS only. However, these differences were not statistically significant.     

Compaction of TiO2 suspension utilizing hydrophilic/hydrophobic transition of cationic thermosensitive polymers

Compaction of TiO2 suspended particles utilizing the hydrophilic/hydrophobic transition of a cationic thermosensitive copolymer of N-isopropylacrylamide (NIPAM) and N-dimethylaminopropylacrylamide (DMAPAA) was examined. The surface of suspended TiO2 particles were sufficiently covered with the adsorbed polymer molecules at room temperature, and the suspension was subsequently heated above the transition temperature of the polymer. The thrusting motion of a plunger was used in order to provide an adequate mechanical force to compact the TiO2 suspended particles. The transition temperature was dependent on the DMAPAA content in the copolymer and the pH of the suspension. The transition temperature increased with increasing DMAPAA content and decreased with increasing pH. While suspended TiO2 particles were not compacted with poly(NIPAM), hard compacted sludge was readily obtained for cationic copolymer even if the content of DMAPAA groups was as low as 0.23 mol%. Furthermore, residual polymer molecules in the supernatant were not detected even if the polymer dosage was increased. These findings were attributed to the hydrophobic interaction of thermosensitive copolymer molecules adsorbed on TiO2 particles.     

Rearranged vibsane-type diterpenes from Viburnum awabuki and photochemical reaction of vibsanin B

Nine new diterpenes, neovibsanin D (1), 7-epi-neovibsanin D (2), 15-O-methylneovibsanin F (3), 14-epi-15-O-methylneovibsanin F (4), 15-O-methyl-18-oxoneovibsanin F (5), 2-O-methylneovibsanin H (6), 2-O-methylneovibsanin I (7), neovibsanin G (8), and 14-epi-neovibsanin G (9), were isolated from a methanol extract of the leaves of Viburnum awabuki. Their structures were elucidated to be uniquely rearranged vibsane-type diterpenes by spectroscopic analyses and comparison of NMR data with those of previously reported vibsane-type diterpenes. In addition, irradiation of vibsanin B (12) in methanol with a high-pressure Hg lump led to the direct formation of neovibsanins A (14) and B (15). These results gave a clue to understanding of the biogenetic interconversion of 11-membered vibsanins into neovibsanins.     

Synthesis and anti-tumor activity of new steroidal nuclear analogues of aragusterol A

3alpha,7alpha-Dihydroxy-5-epiaragusterol A (3) was synthesized from bile acid (cholic acid) as a new steroidal nuclear analogue of antitumor marine steroid aragusterol A. 7alpha-Hydroxyaragusterol A (4) was also derived from xestokerol B. The in vitro anti-proliferative activity of each of these analogues toward KB cells as well as in vivo anti-tumor activity of 5-epiaragusterol A (2) previously synthesized by the authors and 3 were assessed.     

Intermolecular hydrogen bonding of steroid compounds: PFG NMR diffusion study, cold-spray ionization (CSI)-MS and X-ray analysis

An extensive analysis of hydrogen bonding of steroid compounds in diluted solution is preformed by pulsed field gradient (PFG) NMR and cold-spray ionization (CSI)-MS, in the solid state by X-ray crystallographic analysis. The formation of hydrogen bond interaction are quantified and discussed. Although X-ray analysis in the crystalline state and CSI-MS measurement in solution suggested that the observed diffusion coefficient D(obs) of the steroid compounds may vary in accordance with the number of hydrogen bonds, the actual observed D(obs) value determined from the diffusion studies diminished constantly without correlation on the decreasing numbers of hydrogen bonds. Comparison of two different calibration profiles of calculated molecular volume (V(cal)) vs. D(obs), which are obtained from compounds possessing no hydrogen bonding and the steroid compounds, formation of a chain structure (cluster) based on intermolecular hydrogen bonding of the steroid compounds is unambiguously confirmed.     

Formation of GeO2 nanosheets using water thin layers in lamellar phase as a confined reaction field--in situ measurement of SAXS by synchrotron radiation

Highly crystallized GeO2 nanosheets were synthesized by hydrolysis and condensation reactions of germanium alkoxide using a 2-dimensional flat thin lamellar phase water layer containing surfactant molecules at the liquid-liquid interface as a confined reaction field.     

NMR conformational analysis of biosynthetic precursor-type lipid A: monomolecular state and supramolecular assembly

The detailed conformational analysis of a single molecule of the tetraacyl biosynthetic precursor-type lipid A and its characteristic supramolecular assembly in aqueous SDS-micelles are described. Regular molecular arrangements were observed by detailed analysis of the NMR spectra of synthetically pure specimens, including regiospecifically 13C-labeled ones. NMR analysis of a biologically inactive precursor-type analogue with four shorter acyl chains demonstrated its conformational flexibility, indicating the importance of hydrophobic interactions for maintaining the conformation of such molecules.     

Expansion of repertoire of modified DNAs prepared by PCR using KOD Dash DNA polymerase

Thymidine analogues bearing a variety of functional groups at the C5-position via an amino-linker arm were prepared and the substrate activity for PCR using thermophilic KOD Dash DNA polymerase was examined. The enzyme accepted the thymidine analogues bearing pyridine, imidazole, biotin, a cationic-charged guanidinium, a cationic-charged amino, mercaptopyridyl and phenanthrolne groups at the C5-position, forming the corresponding PCR product. However, a thymidine analogue bearing a carboxyl group at the C5-position was a poor substrate and the corresponding PCR products could not be obtained. The thymidine analogue bearing a mercapto group was also a poor substrate for the enzyme, because it dimerized by disulfide linkage under PCR conditions. The enzyme hardly accepts the thymidine analogues with a negatively-charged carboxyl group or a bulky group as a substrate. KOD Dash DNA polymerase, having a broader substrate specificity than any other DNA polymerase, will expand the variety of modified DNAs that can be prepared by PCR.     

High resolution-separation of DNA bands by electrophoresis with a long gel in a fluorescence-detection DNA sequencer.

A high-resolution separation of DNA bands is achieved by electrophoresis with a long gel in DNA base sequencing using fluorescence detection. We separate 760 and 761 base DNA fragments using the 93 cm migration electrophoresis optimized for the separation of DNA bands. A T7 DNA polymerase and an Mn++ buffer are used in sequencing reactions to obtain fluorescence peaks of uniform strength, and the peak areas in the spectrum are used for recognizing the peak number in a cluster of successive peaks. This method is successfully applied to the DNA fragment spectrum obtained by 93 cm migration electrophoresis, which results in a single-band differentiation of bands of 1040 base DNA.