Activity of artificial mutant variants of human growth hormone deficient in a disulfide bond between Cys53 and Cys165

In order to understand the role of Cys53 and Cys165 of human growth hormone (hGH) in receptor-binding and biological activity, artificial mutant variants of hGH were prepared in Escherichia coli by in vitro mutagenesis. Variants of hGH were constructed by replacement of Cys165 with Ala ([Ala165]hGH) or Ser ([Ser165]hGH), by replacement of Cys53 with Ala ([Ala53]hGH), by replacement of Cys53 and Cys165 with Ala ([Ala53, Ala165]hGH), or by replacement of Cys53 with Ala and Cys165 with Ser ([Ala53,Ser165]hGH). All of the variants constructed as well as reduced hGH exhibited less biological activity than that of intact hGH, and the decreases in biological activity were almost equal, as measured by a sensitive biological assay for growth hormone: adipose conversion assay using 3T3-F442A cells. These variants also showed less receptor-binding activity than that of intact hGH. These results suggest that it is possible neither the residue Cys53 nor Cys165 is directly involved in the receptor binding, and that the disulfide bridge between Cys53 and Cys165 in hGH may not always be crucial for the biological activity, though necessary to express full hGH activity.     

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.     

The study of electron beam flue gas treatment for coal-fired thermal plant in Japan

The fundamental research work with simulated coal-fired flue gas was performed in JAERI to get basic data for electron beam treatment of flue gas from thermal power plants in Japan. The standard condition of the experiments was set to be the same as that of next large scale pilot test in Nagoya. The concentrations of NO_x and SO_x were 225 ppm and 800 ppm, respectively. The temperature of the system was 65°C. The effect of multiple irradiation was observed for NO_x removal. The target SO_x and NO_x removals (94% and 80%, respectively) with low NH₃ leakage (less than 10 ppm) were achieved at 9 kGy irradiation with 0.9 NH₃ stoichiometry during 7 hours continuous operation. The facility for the pilot plant (12,000 Nm³/hr) has just built at the site of Shin-Nagoya power plant of Chubu Electric Power Company and will be started in full operation in November 1992.     

Resolution of lymphocyte subpopulations derived from rat spleen by polyamine-graft-PHEMA copolymer

The retention behavior of lymphocyte subpopulations, B cell, T cell and null cell, derived from rat spleen to polyamine-graft-poly(2-hydroxyethyl methacrylate) copolymer (HA) surface was investigated, focusing on the conformational transition of the polyamine side chain as well as the protonation of amino groups in the polyamine grafts. Furthermore, the availability of HA was discussed as a column adsorbent for separation of lymphocyte subpopulations derived from spleen. The conformational transition of polyamine grafts significantly influenced the mode of retention of lymphocyte subpopulations. When polyamine grafts existed in an aggregated conformation (protonatin degree α < 0.5), the retention of lymphocyte subpopulations was decreased in the order B cell> null cell> T cell. On the other hand, when polyamine existed in an extended conformation into the aqueous interior from the matrix interface (α > 0.5), T cell retention became greater than null cell retention, resulting in a decreased B cell> T cell> null cell order. These results indicate that the differential retention of spleen lymphocyte subpopulations is attributed to their differential responses to the change in matrix interface accompanied by the protonation of amino groups. Furthermore, spleen lymphocytes were compared with lymph node lymphocytes in terms of resolution efficacy by an HA copolymer column.     

Time evolution of density fluctuation in the supercritical region. 2. Comparison of hydrogen- and non-hydrogen-bonded fluids

The time evolution of the density fluctuation of molecules is investigated by dynamic light scattering in six neat fluids in supercritical states. This study is the first to compare the dynamics of density inhomogeneity between hydrogen- and non-hydrogen-bonded fluids. Supercritical methanol and ethanol are used as hydrogen-bonded fluids, whereas four non-hydrogen-bonded fluids were used: CHF(3), C(2)H(4), CO(2), and Xe. We measure the time correlation function of the density fluctuation of each fluid at the same reduced temperatures and densities and investigate the relationship between the dynamic and static density inhomogeneities of those supercritical fluids. In all cases, the profile of the time correlation function of the density fluctuation is characterized by a single-exponential function, whose decay is responsible for the dynamics characterized by hydrodynamic conditions. We obtain correlation times from the time correlation function and discuss dynamic and static inhomogeneity using the Kawasaki theory and the Landau-Placzek theory. While the correlation times in the six fluids show noncoincidence, those values agree well with each other except for the supercritical alcohols when scaled to a dimensionless parameter. Although the principle of corresponding state is observed in the non-hydrogen-bonded fluids, both the supercritical methanol and ethanol deviate from that principle. This deviation is attributed to the presence of hydrogen bonding among alcohol molecules at high temperature and low density. The average cluster size of each fluid is estimated under the same thermodynamic conditions, and it is shown that the clusters of supercritical alcohols are on average 1.5-1.7 times larger than those of the four non-hydrogen-bonded fluids. Moreover, the thermal diffusivity of each neat fluid is obtained over wide ranges of density and temperature.     

CpRuIIPF6/quinaldic acid-catalyzed chemoselective allyl ether cleavage. A simple and practical method for hydroxyl deprotection

A cationic CpRu(II) complex in combination with quinaldic acid shows high reactivity and chemoselectivity for the catalytic deprotection of hydroxyl groups protected as allyl ethers. The catalyst operates in alcoholic solvents without the need for any additional nucleophiles, satisfying the practical requirements of operational simplicity, safety, and environmental friendliness. The wide applicability of this deprotection strategy to a variety of multifunctional molecules, including peptides and nucleosides, may provide new opportunities in protective group chemistry. [structure: see text]     

Radiation-induced emission from golden hamster embryo cells

Emission from high-energy-electron-irradiated golden hamster embryo (GHE) cells has been studied over the temperature range 12–300 K both by a one-shot-single-photon-counting method and by photocurrent measurements with an oscilloscope. Emission from the irradiated phosphate buffered saline (PBS) also has been studied. The emission spectra from PBS at 12 and 77 K show a maximum around 330 and 380 nm, respectively, which are the same spectra as those from irradiated pure H₂O. The emission from irradiated GHE consists of the new band at 480 nm in addition to the emission from H₂O. The 480 nm emission is observed at the temperature range of 12–300 K, though the emission at 300 K is much lower than that at low temperature. The 480 nm emission is ascribed to the transition from excited organic substances in GHE cells. The intensity of 480 nm emission at 300 K increases linearly with increasing irradiation-dose in the range of 11–600 Gy.     

γ-Radiolysis of 5-fluorouracil and 5-fluorouridine derivatives having sulfur-containing substituents

γ-Radiolysis reactions of eight 5-fluorouracil (5-FU) derivatives having sulfonyl group-containing substituents at the 1-position and five 5-fluorouridine (5-FUR) derivatives having thioureido group-containing substituents were studied under the conditions where hydrated electron (e_aq^?) and hydroxyl radical (HO·) become the principal reactive species. The 5-FU and 5-FUR derivatives were radiolyzed to give 5-FU and 5-FUR, respectively. The efficiency of the reactions depended upon the nature of reactive species and also upon the nature of substituents. The reactivity features of the γ-radiolysis reactions are discussed.     

Cation-pi interactions of a thiocarbonyl group and a carbonyl group with a pyridinium nucleus

Attractive interactions between a thiocarbonyl group and a pyridinium nucleus, and between a carbonyl group and a pyridinium nucleus have been proven by (1)H and (13)C NMR studies, UV-vis spectral analyses, and X-ray crystallographic analyses of nicotinic amides 1 and 3, and pyridinium salts 2 and 4. Comparison of the Deltadelta values, which are the differences in the chemical shifts with reference compounds 5 or 6, showed that the absolute Deltadelta values of 2 and 4 are much larger than those of 1 and 3. In the UV-vis spectra, the n-->pi absorption of the C=S group of 2a exhibited a significant blue shift in CHCl(3). X-ray crystallographic analysis of 1-4 clearly showed that the C=S group of 2a and the C=O group of 4 are very close to the pyridinium moiety compared to the case of 1 and 3. In addition, the X-ray crystal packing structure of 2a showed the C=S group is sandwiched between two pyridinium rings. These experimental results strongly suggested the existence of attractive (C=S)...Py(+) and (C=O)...Py(+) interactions in solution and in crystal. The optimized geometries of 1 and 2 calculated at the HF/6-311G level are in good agreement with their X-ray geometries. MP2/6-311G calculations for the model systems of pyridinium salts 2 and 4 predicted that the electrostatic and induction energies are the major source of the attractive interactions. Since the larger contribution of electrostatic and induction interactions are characteristic features of cation-pi interactions, the (C=S)...Py(+) and (C=O)...Py(+) interactions would be classified as a cation-pi interaction.     

Two-carbon ring expansion of cyclobutanone skeletons by nickel-catalyzed intermolecular alkyne insertion

The reaction of cyclobutanone with an alkyne in the presence of a nickel(0) catalyst formally achieves intermolecular alkyne insertion between the carbonyl carbon and the α-carbon of a cyclobutanone, providing a six-membered carbocyclic skeleton.