Polymerization of ethylene and propylene initiated by milled alumina powder

Generation of free radicals (mechano-radicals) by the milling of alumina powder at 77 K was demonstrated by ESR. After milling of alumina in the presence of ethylene (simultaneous milling) at 77 K, polyethylene-propagating radicals instead of the alumina mechano-radicals were detected by ESR. Also the contact of ethylene with the milled alumina converted alumina mechano-radicals into polyethylene propagating radicals at a temperature above the melting point of ethylene. The products extracted by hot toluene from the simultaneous milling were identified by IR to be polyethylene, and their molecular weights were roughly 10,000. The residues after the extraction were bonded with the alumina. Polypropylene was also produced by a similar method of milling of alumina in the presence of propylene. The obtained polyproylene was atactic, and its molecular weight was about 400.     

Actin binding to cross-linked 10 S smooth muscle myosin and 9 S heavy meromyosin

Unphosphorylated gizzard myosin and heavy meromyosin were cross linked in the 10 S and 9 S states, respectively, by the cleavable cross linker, 3,3'-dithiobis (sulfosuccinimidyl-propionate) (DTSSP). The 10 S to 6 S transition for cross-linked 10 S myosin appeared to cease; myosin appeared to remain in the 10 S state from measurements of viscosity and Mg(2+)-ATPase activity. The loss of the transition for cross-linked 9 S heavy meromyosin (HMM) was also indicated by Mg(2+)-ATPase activity. The cross links were cleaved by incubation with 50 mM dithiothreitol. From direct binding measurements, the estimated Kd's of actin to cross-linked and control heavy meromyosin were 167 and 16 microM, respectively. The binding affinity of cross-linked HMM to actin was restored to the control level by dithiothreitol.     

E.s.r. study of vanadyl complexes in various carbonaceous materials at high temperature

E.s.r. spectra of vanadyl complexes in various carbonaceous materials were measured in a range between room temperature and 435 °C. The e.s.r. spectrum of vanadyl complex doped in Taching reduced crude was a slow tumbling pattern at temperatures between 60 °C and 225 °C. By the rapid freezing technique, it became clear that the vanadyl complex in Taching residue was oriented to the magnetic field in its temperature range. Further, activation energies for rotations of vanadyl complexes in those carbonaceous materials were estimated from Arrhenius plots of the correlation times. Those carbonaceous materials were classified into two groups according to values of the activation energies. This classification was consistent with that based on mesophase textures of the cokes made from them.     

Study of carbonaceous mesophase through the e.s.r. spectra of vanadyl chelates

The behaviour of vanadyl chelate complexes in Iranian heavy oil and ethylene tar pitch during the carbonization process has been investigated by the e.s.r. technique to obtain information on the mesophase transformation. Activation energies for rotation of chelates incorporated with aromatic lamellae, and ordering parameters, are estimated from correlation times and intensities of e.s.r. spectra. The molecular plane of the chelates incorporated into the mesophase was found to be oriented parallel to the applied field. The value of activation energy is higher for a mesophase of small size than for a larger one.     

“Click Peptide“: pH‐Triggered in Situ Production and Aggregation of Monomer Aβ1–42

Into neutral : We demonstrate the unique features of a pH click peptide based on an O‐acyl isopeptide method. Under acidic conditions, the click peptide remains in a monomeric form. Upon increase of the pH to 7.4, the click peptide is quickly able to convert into Aβ1–42 through an O‐to‐N intramolecular acyl migration. Further study using this pH click peptide would elucidate the pathological role of Aβ1–42 in Alzheimer's disease.

     

Molecular modeling of single polypeptide chain of calcium-binding protein p26olf from dimeric S100B()

P26olf from olfactory tissue of frog, which may be involvedin olfactory transduction or adaptation, is a Ca²⁺-binding proteinwith 217 amino acids. The p26olf molecule contains two homologousparts consisting of the N-terminal half with amino acids 1–109and the C-terminal half with amino acids 110–217. Eachhalf resembles S100 protein with about 100 amino acids and containstwo helix–loop–helix Ca²⁺-binding structural motifsknown as EF-hands: a normal EF-hand at the C-terminus and apseudo EF-hand at the N-terminus. Multiple alignment of thetwo S100-like domains of p26olf with 18 S100 proteins indicatedthat the C-terminal putative EF-hand of each domain containsa four-residue insertion when compared with the typical EF-handmotifs in the S100 protein, while the N-terminal EF-hand ishomologous to its pseudo EF-hand. We constructed a three-dimensionalmodel of the p26olf molecule based on results of the multiplealignment and NMR structures of dimeric S100B(ßß)in the Ca²⁺-free state. The predicted structure of the p26olfsingle polypeptide chain satisfactorily adopts a folding patternremarkably similar to dimeric S100B(ßß). Each domainof p26olf consists of a unicornate-type four-helix bundle andthey interact with each other in an antiparallel manner formingan X-type four-helix bundle between the two domains. The twoS100-like domains of p26olf are linked by a loop with no sterichindrance, suggesting that this loop might play an importantrole in the function of p26olf. The circular dichroism spectraldata support the predicted structure of p26olf and indicatethat Ca²⁺-dependent conformational changes occur. Since theC-terminal putative EF-hand of each domain fully keeps the helix–loop–helixmotif having a longer Ca²⁺-binding loop, regardless of the four-residueinsertion, we propose that it is a new, novel EF-hand, althoughit is unclear whether this EF-hand binds Ca²⁺. P26olf is a newmember of the S100 protein family.     

Effects of prophylactic antibiotic agent on interleukin-6 level in open chest surgery--comparison between imipenem and flomoxef

The blood of diabetics often shows enhanced peroxidative reactions and non-enzymatic glycosylation, or glycation. These features should also be manifest in the vitreous in diabetic eyes. I quantitated the level of superoxide dismutase (SOD) in the serum and the vitreous in 22 eyes of 23 diabetics and in 16 eyes of 16 nondiabetics. The total amount of serum SOD was the same in both groups. There was a significant decrease in SOD activity in the diabetic vitreous (p < 0.05). The diabetic vitreous also showed increases in glycated Cu, Zn-SOD and glycated protein. The level of lipid peroxidases was significantly increased in the diabetic vitreous (p < 0.05). These findings suggest that glycation is enhanced in the diabetic vitreous resulting in collapse of active oxygen scavenging and in progressed peroxidation.     

Polymerizations of ethylene and propylene initiated by milled metallic oxides. II. Characterizations of the mechanochemically produced polymers

Polyethylene was mechanochemically produced by milling of alumina powder at room temperature in the presence of ethylene monomer. Nearly 50% of the produced polyethylene was chemically bonded with the matrix of the alumina. The other 50% of the polymer was extracted by the organic solvents. The polyethylene extracted by the hot n-heptane was characterized as having a structure similar to that of the branched polyethylene of low density, and the toluene extracted polyethylene had a structure similar to that of the high density polyethylene. The molecular weights of the mechanochemically produced polyethylene were found to distribute from 10² to 10⁶ by gel permeation chromatography. The weight average molecular weight was estimated as 260,000 after the 3 days milling. Mechanochemical polymerization of ethylene was also demonstrated by milling of silica in the presence of ethylene monomer. Polymerization of propylene by milling of alumina under propylene atmosphere was performed. The obtained polymer was found to be an atactic by IR measurement and the molecular weight of the extracted product was determined as ? 400 by the vapor pressure osmometer.     

Copolymerizations initiated by mechano-radicals on particle surfaces of poly(tetrafluoroethylene)

Mechanical fracture of solid poly(tetrafluoroethylene) (PTFE) produces main-chain scissions of the polymer, and free radicals, called mechano-radicals, are trapped on fresh surfaces generated by the fracture. These radical conversions were verified by ESR observation when several monomers—methylmethacrylate, vinylacetate, and ethylene—were brought into contact with these mechano-radical, and the copolymerizations of PTFE with these monomers were demonstrated. It was found that a new surface property, wettability of water, was added to the solid PTFE by the copolymerization with vinyl acetate, although the bulk nature of PTFE was not changed.