Prospective study to assess the clinical efficacy of bone scintigraphy--some analyses of clinical data

The value of preoperative bone scans in patients with primary breast and prostate cancer was evaluated prospectively. Of 414 patients with breast cancer, clinical stage I is 14, II is 219, IIIA is 59, IIIB is 39 and IV is 14. Of 88 patients with prostate cancer, clinical stage I is 14, II is 15, III is 18 and IV is 41. 11 percent of patients with breast cancer and 54 percent of patients with prostate cancer had bone metastases. Clavicle, ribs, thoracic spine, lumbar spine and pelvis metastasized most frequently. The incidences of bone metastases were 18.4% with Scirrhous carcinoma, 15.4% with Medullary tubular carcinoma and 3.8% with Papillotubular carcinoma. The methodology and results of ROC analysis were described in our other papers. Some results of data analysis were described in this paper.     

Isomorphic electron orbitals for vibronic flexibility in a cyclopropenyl radical molecular device

Summary The vibronic character of this molecular device has been studied using isomorphic electron orbitals. The leading role of the softest vibrational mode for the electron transport process is stressed by the quantum mechanical treatment of the rearrangement operator. The theory was used to investigate the possible function of the soliton valve, which has been suggested as a switching tip. The electronic flexibility of the cyclopropenyl radical with respect to molecular vibrations, which is important for the function of the molecular device, is well characterized by the hardness and softness of the electron structure in terms of the orbital energy-occupation number correlation diagram.     

A quantum chemical study of interchain hopping model of negatively charged solitons in polyacetylene

Phonon-assisted interchain hopping of negatively charged solitons in polyacetylene has been studied using a local chemical reaction model CH + CH₄ → CH₄ + CH. Quantum chemical characteristics of the electron transfer process have been analyzed in terms of the dynamic electron density and the mutual polarization moment. The CH stretching vibrational motion of CH₄, which is a local model of the sp³ defect, has been found to play a significant role for the electron transfer. The excitation of the corresponding vibrational mode of the sp³ defect would promote the interchain hopping of the charged soliton. The electron transfer process has also been studied in terms of the “regional” density functional theory. It has been shown that the driving force of the electron transfer is represented by the regional chemical potentials.     

Preparation of 2-fluoromalonic esters and related compounds from hexafluoropropene

Dimethyl and diethyl fluoromalonates were prepared from hexafluoropropene by its exhaustive alcoholysis or alternatively its ammonolysis and alcoholysis. Fluoromalonates thus obtained or their alkylated derivatives were condensed with o-phenylenediamine or its substituted derivatives to give a number of 1H-3-fluoro-1,5-dibenzodiazepin-2,4(3H,5H)-diones.     

Photochemically generated silicon-carbon double-bonded intermediates VIII. Photolysis of phenyldisilane derivatives in the presence of olefins

Photolysis of phenylpentamethyldisilane, 1,1-diphenyltetramethyldisilane and 1-isopropyl-1-phenyltetramethyldisilane in the presence of a wide variety of olefins has been studied. All reactions investigated, with the exception of those with 1-methylcyclohexene and tetramethylethylene, afforded the corresponding 1/1 addition products. Yields of the adducts depended highly on the structure of the olefins used. In the photolysis of phenylpentamethyldisilane in the presence of an equimolar mixture of 1,1- and 1,2-bis(trimethylsilyl)ethene under competitive reaction conditions, the main product was the one arising from the 1,1-isomer. A possible mechanism for the process of addition of olefin to the photochemically generated silicon-carbon double-bonded intermediate (A) is discussed.     

Amphotericin B covalent dimers forming sterol-dependent ion-permeable membrane channels

Polyenemacrolides such as amphotericin B (AmB) were thought to assemble together and form an ion channel across plasma membranes. Their antimicrobial activity has been accounted for by this assemblage, whose stability and activity are dependent on sterol constituents of lipid bilayer membranes. The structure of this channel-like assemblage formed in biomembranes has been a target of extensive investigations for a long time. For the first step to this goal, we prepared several AmB dimers with various linkers and tested for their channel-forming activity. Among these, AmB dimers that bore an aminoalkyl-dicarboxylate tether covalently linked between amino groups of AmB showed potent hemolytic activity. Furthermore, K+ influx actions monitored by measuring the pH of the liposome lumen by 31P NMR revealed that the dimers formed the molecular assemblage similar to that of AmB in phospholipid membrane. Judging from changes in 31P NMR spectra, the dimers appeared to induce "all-or-none"-type ion flux across the liposome membrane in the presence of ergosterol, which suggested that the ion channel formed by ergosterol/dimer is similar to that of AmB. With these data in hand, we are now trying to elucidate the structure of the ion-channel complex by making the labeled conjugates of AmB for NMR measurements.     

Change of concentrations of trace elements and protein contents in the liver of zinc deficient mice

The concentrations of essential trace elements and proteins in cytosolic fraction of hepatic cells of mice fed with Zn-deficient diet (Zn-def, mice) and control were determined by ICP-MS and BCA protein assay method, respectively, after division into forty fractions by gel filtration chromatography. The concentrations of zinc and proteins decreased in the 14–17th fractions of Zn-def, mice, whereas cobalt concentrations increased in the 14, 17, and 18th fractions. However, no significant differences were found on the gel after SDS-PAGE for the 12–21st fractions, although the BCA protein assay date showed the decrease of protein amounts in 13–15th fractions of Zn-def. mice.     

Efficient photocleavage of DNA by cationic porphyrin-acridine hybrids with the effective length of diamino alkyl linkage

Positively charged porphyrins bearing an acridine with various lengths of diamino alkyl linkage, 5-[4-[(6-chloro-2-methoxy-9-acridyl)aminoalkylaminocarbonyl]phenyl]-10,15,20-tris(4-N-methylpyridiniumyl)porphine triiodide, alkyl=ethyl, butyl, hexyl, or octyl, were synthesized. They exhibited more enhanced photocleavage activity of pUC18 plasmid DNA than TMPyP, meso-tetrakis(4-N-methylpyridiniumyl)porphine, which is well known to bind to DNA tightly and to cleave DNA effectively; the hybrid linked with the hexamethylene chain showed particularly high activity. An equilibrium dialysis experiment demonstrated that the binding ability of the hybrids to calf thymus (CT) DNA correlated quantitatively with the photocleavage activity. The lack of the substantial red-shift of the Soret maxima of the hybrids through the titration with CTDNA denied the intercalative binding of the porphyrin part. In their circular dichroism (CD) spectral change on binding to CTDNA, two negative peaks appeared at 275 nm and at 285-290 nm in the UV range. The latter negative peak was observed for hybrids, but not for TMPyP, and thus we assigned it to induced CD (ICD) derived from intercalation of acridine chromophore. In the visible range, the hybrids showed only a positive peak around their Soret maxima, and this feature suggested the porphyrin moiety lay in the DNA groove. In addition, the length of the linker markedly influenced the ellipticity of their visible ICD, suggesting that the proximity of the porphyrin moiety to DNA was greatly affected by the linker.     

Ligand Substitution Reaction of Bis(ethylenediamine)glycinatocobalt(III) Complex with Ethylenediamine Catalyzed by the Photo-excited Tris(2,2′-bipyridine)ruthenium(II) Complex

Substitution reaction with ethylenediamine of coordinated glycinate ligand in bis(ethylenediamine)-glycinatocobalt(III) complex has been studied in the presence of photo-excited tris(2,2′-bipyridine)ruthenium(II) complex in alkaline aqueous solution (buffered around pH 12) containing 1.0M chloride ion at 25°C. VIS absorption and CD spectra were used for the racemate and the optically active isomers of the Co(III) complexes, respectively. The reaction was catalyzed by the excited Ru(II) complex to give tris(ethylenediamine)cobalt(III) complex. Mechanism of the ligand-substitution reaction and role of the excited Ru(II) complex were discussed.     

Recovery and refining of au by gold-cyanide ion biosorption using animal fibrous proteins

Animal fibrous proteins (AFPs) such as egg-shell membrane (ESM), chicken feather (CF), wool, silk, or elastin are an intricate network of stable and water-insoluble fibers with high surface area and are abundant bioresources. Every AFP tested was found to accumulate gold-cyanide ion from aqueous solutions in high yield, depending on pH and some other parameters. Gold-cyanide ion is adsorbed by AFP at low pH range, with maximum binding observed at approx pH 2.0. Under the certain conditions, gold-cyanide ion was accumulated up to 8.6, 7.1, 9.8, 2.4, and 3.9% of dry weight on ESM, CF, wool, silk, and elastin, respectively. In the case of ESM, it was found that ESM removed gold-cyanide ion almost quantitatively and almost all the gold uptake by ESM was easily desorbed with 0.1M NaOH. ESM can be used repeatedly for the process of gold adsorption-desorption. The gold-biosorptive capacity of ESM that was chemically modified with glutaraldehyde was higher than that of control. In column procedure, ESM packed on column removed gold-cyanide ion from the dilute aqueous solution to extremely low concentrations (nondetectable concentration of below 1 ppb)