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The catalytic behavior of fluorinated bis(phenoxy−imine)titanium complexes bearing a series of substituents ortho to the phenoxy oxygen was studied for ethylene and ethylene/higher α-olefin (i.e., 1-hexene, 1-octene, and 1-decene) (co)polymerizations. Independent of the magnitude of steric bulk of the ortho-substituent, all the complexes that were investigated produced polyethylenes (PEs) and ethylene/higher α-olefin copolymers with very narrow molecular weight distributions [e.g., PEs, Mw/Mn = 1.05−1.16, Mn = 44000−412000; ethylene/1-hexene copolymers, Mw/Mn = 1.07−1.19, Mn = 49000−102000, 1-hexene content 3.2−22.6 mol %], indicative of living polymerization. The incorporation ability for higher α-olefins is highly dependent on the nature of the ortho-substituent, and Ti complexes with a sterically less encumbered ortho-substituent incorporated a higher amount of higher α-olefins. A number of unique block copolymers consisting of highly linear PE and ethylene/1-hexene copolymer segments were prepared using one of the living catalysts with enhanced incorporating capability for higher α-olefins. These block copolymers exhibited lower peak melting temperatures (Tm) relative to the corresponding homo-PE. The molecular weight and 1-hexene content of the copolymer segment had a considerable effect on the Tm values of the resultant block copolymers. A polyethylene-b-poly(ethylene-co-1-hexene) (Mw = 79900, Mw/Mn = 1.26, 1-hexene content 4.3 mol %) possessed unique tensile properties with a good combination of extensibility and toughness compared to the corresponding blend and random (co)polymers.

Abstract: Background: We examined the factors of delayed enhancement of hepatocellular carcinoma (HCC) on dynamic computed tomography (CT). Methods: Dynamic CT and angiography were compared in 113 patients who had undergone transcatheter arterial chemoembolization or transcatheter arterial chemoinfusion and were suspected of developing new HCCs. Results: Eight of 113 patients had HCC nodules that enhanced gradually from the arterial phase to the portal venous phase on dynamic CT and were fed by extrahepatic arteries on angiography. The feeding artery was an omental branch of the splenic artery in one lesion, an omental branch of the gastroduodenal artery in five, and the intercostal artery in two. Conclusion: We believe that the recurrence of HCCs delayed enhancement on dynamic CT because the hepatic artery was hidden and long narrow extrahepatic collaterals fed the tumor.

New titanium complexes 1−4 having two nonsymmetric bidentate pyrrolide−imine chelate ligands, [2-(RNCH)C4H3N]2TiCl2 (1, R = Ph; 2, R = Et; 3, R = n-hexyl; 4, R = cyclohexyl), are prepared in good yields from the lithium salt of the corresponding ligands and TiCl4. Complex 1 is suggested by DFT calculations to adopt a distorted-octahedral structure in which the two pyrrolide-N atoms are situated in trans positions, while the two imine-N atoms and the two Cl atoms are located cis to one another. The spatial disposition elucidated by X-ray crystallographic analysis of complex 1 is consistent with the preferred structure predicted by DFT calculations. The molecular structures of complexes 2 and 4 established by X-ray analyses are very similar to that of complex 1. DFT calculations suggest that an active species derived from complex 1, for ethylene polymerization, possesses cis-located active sites trans to the imine-N atoms. These complexes were investigated as ethylene polymerization catalysts. Using methylalumoxane (MAO) as a cocatalyst, these complexes display very high activities and produce high-molecular-weight polyethylenes. Among them, complex 4 exhibits the highest activity (14 100 kg of polymer/((mol of Ti) h) comparable to that of Cp2TiCl2 with a very high molecular weight (Mv) value of 2 601 000. Alternatively, using Ph3CB(C6F5)4/i-Bu3Al as a cocatalyst, these complexes produce ultrahigh-molecular-weight polyethylenes (Mv > 4 000 000) with high activities (1500−2000 kg of polymer/((mol of Ti)/h).

Heterologous protein expression levels in Saccharomyces cerevisiaefermentations are highly dependent on the susceptibility to endogenous yeast proteases. Small peptides, such as glucagon and glucagon-like-peptides (GLP-1 and GLP-2), featuring an open structure are particularly accessible for proteolytic degradation during fermentation. Therefore, homogeneous products cannot be obtained. The most sensitive residues are found at basic amino acid residues in the peptide sequence. These heterologous peptides are degraded mainly by the YPS1-encoded aspartic protease, yapsin1, when produced in the yeast. In this article, distinct degradation products were analyzed by HPLC and mass spectrometry, and high yield of the heterologous peptide production has been achieved by the disruption of the YPS1gene (previously called YAP3). By this technique, high yield continuous fermentation of glucagon in S. cerevisiaeis now possible.

Prolactin receptors were purified to homogeneity by two affinity chromatography steps using concanavalin A-Sepharose and human growth hormone (hGH)-Sepharose. The purified receptors showed specificity and high affinity for lactogenic hormones and a binding capacity of 20 nmol/mg of protein. Sodium dodecyl sulfate (SDS)-polyacrylamide gel electrophoresis analysis revealed that purified receptors were composed of two major protein bands of Mr = 41,000 and 88,000, which were identified as radioactive bands by binding of 125I-hGH to blotted renatured receptors and by autoradiogram of free and 125I-radiolabeled purified receptors. Autoradiographic analysis of SDS-polyacrylamide gel electrophoresis of cross-linked 125I-hGH-receptor or hGH-125I-iodinated receptor complexes showed two radioactive bands of Mr = 63,000 and 106,000. Analysis of the free receptors by high performance liquid chromatography using Superose 12 revealed two peaks of binding activity for 125I-hGH eluting in the positions of Mr approximately 150,000 and 250,000. After cross-linking with 125I-hGH, SDS-polyacrylamide gel electrophoresis analysis revealed that both peak fractions contained two binding species with Mr = 63,000 and 106,000. Chromatography of 125I-hGH-receptor complexes showed two radioactive fractions with approximate Mr approximately 180,000 and 300,000. The treatment of 125I-iodinated receptors with SDS and reductant resulted in the dissociation of the higher Mr form into the lower Mr form upon gel filtration. Chromatofocusing of free receptors showed three isoforms with pI 4.0, 5.0, and 5.3. These results indicate that detergent-solubilized prolactin receptors appear to be aggregated forms of holoreceptor containing two binding species of Mr = 41,000 +/- 2,000 and 88,000 +/- 3,000.

A procedure for the calculation of molecular properties in the full quantum mechanical treatment is presented. We formulate the non-Born–Oppenheimer density functional theory and propose its numerical scheme. We numerically calculate the energy, particle densities, interparticle distance, and (hyper)polarizability of the hydrogen molecule and its isotopes using this method and discuss isotope effects on the physical properties. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 70: 659–669, 1998

The binding of EGTA and EDTA to alpha-lactalbumin, first demonstrated by Kronman and Bratcher (Kronman, M. J., and Bratcher, S. C. (1983) J. Biol. Chem. 258, 5707-5709) and afterwards regarded as a significant source of error in estimating the binding constant of Ca2+ to the protein, has been investigated by comparison of the thermal unfolding curves of the protein in the absence and presence of the chelators and also by measuring the NMR spectra of the protein, the chelators, and the protein-chelator mixtures. The unfolding curve in the presence of a large excess of each chelator has been found to be identical to that in the absence of chelator, indicating that there is essentially no interaction between the chelators and alpha-lactalbumin. The NMR results have also supported this conclusion, and the innocuous character of these chelators as metal-ion buffers in studying the Ca2+-binding properties of alpha-lactalbumin is demonstrated. In order to re-examine the binding constant for Ca2+ of alpha-lactalbumin without the aid of chelating metal-ion buffers, the thermal unfolding curve of the protein in the presence of 0.1 mM excess Ca2+ but without chelators has been compared with the unfolding curve in the absence of Ca2+ at a constant concentration of Na+ (0.010 or 0.10 M) at pH 7.0. The binding constant of alpha-lactalbumin can be calculated from the increment of melting temperature caused by the presence of Ca2+ and from the enthalpy and heat capacity changes in the unfolding. Because Ca2+ binding to the unfolded protein can be neglected under the conditions employed, the binding constant evaluated corresponds to the binding constant to protein that has native structure. The constant obtained is 3-5 X 10(9) M-1 after corrections for binding of Na+ to the protein and for ionic strength, and this shows excellent agreement with the corresponding value previously estimated (2.9 +/- 1.0 X 10(9) M-1), although the latter value was obtained in the presence of EDTA. The apparent Ca2+-binding constant that has been discussed in most previous studies, without taking account of the folding-unfolding equilibrium associated with the binding process, also depends on the concentration of monovalent cations such as Na+, and the present results lead to values of 1.5 X 10(8) and 8.7 X 10(6) M-1 at 0.01 and 0.1 M Na+, respectively.

Rats and dogs were given a single 20-mg/kg dose of [14C]carumonam intramuscularly or intravenously. In rats, the level in plasma of [14C]carumonam administered intramuscularly peaked (29.1 micrograms/ml) 15 min after dosing and then declined with an apparent elimination half-life of 16.2 min. Intramuscular injection of [14C]carumonam to dogs gave a peak level (36.8 micrograms/ml) in plasma at 20 min and an apparent elimination half-life of 51.7 min. After administration of the intravenous dose, apparent elimination half-lives were 13.1 and 52.7 min in rats and dogs, respectively. In both animals, the radioactivity in plasma was made up largely (greater than 80%) of unchanged carumonam, which was protein bound to only a small extent. In rats given [14C]carumonam intramuscularly, radioactivity was distributed widely in tissues, with relatively high concentrations in the kidney and liver. The radioactivity concentration in the rat fetus was relatively low, as was that in milk. In both rats and dogs carumonam did not undergo extensive metabolism; the most prominent metabolite was AMA-1294, the compound resulting from beta-lactam ring hydrolysis. [14C]carumonam and metabolites were mostly eliminated from the bodies within 72 h in rats and 120 h in dogs. In both animals, a large amount of the dosed radioactivity was excreted in the urine largely as unchanged antibiotic. The remainder was eliminated in the feces via bile. AMA-1294 was eliminated from the bodies of rats and dogs at a considerably slower rate than was unchanged carumonam. In rats, [14C]carumonam was eliminated by both glomerular filtration (67%) and tubular secretion (33%); the renal elimination of [14C]AMA-1294 was only by glomerular filtration.

Purified feline leukemia virus, UV light-inactivated feline leukemia virus, and a synthetic peptide (CKS-17) homologous to a well-conserved region of the transmembrane components of several human and animal retroviruses were each studied for their effects on IgG production by feline peripheral blood lymphocytes. Using a reverse hemolytic plaque assay, both the viable virus and the UV-inactivated feline leukemia virus, but not the CKS-17, activated B lymphocytes to secrete IgG. When staphylococcal protein A, a polyclonal B-cell activator, was used to stimulate IgG synthesis by feline lymphocytes, the viable virus, the UV-inactivated virus, and the CKS-17 peptide each strongly suppressed IgG secretion without compromising viability of the lymphocytes. These findings suggest that the immunosuppressive influences of feline leukemia virus on immunoglobulin synthesis may reside in a conserved portion of the envelope glycoprotein that includes the region homologous to CKS-17.

Abstract: We report a case of cerebral air embolism resulting from accidental air infection during cerebral angiography. A 60-year-old man was accidentally injected with air via the left subclavian artery. Angiography demonstrated air within the basilar artery. The patient showed signs of posterior circulation ischaemia (confusion, blindness, gaze palsy and hemiparesis). However, MRI, including diffusion-weighted imaging, showed no abnormality 4 h later. The patient was treated with hyperbaric oxygen within 5 h of the embolism. All symptoms and signs resolved completely within a week.

Abstract We report on the usefulness of spiral computed tomography (CT) with 3-dimensional (3D) reconstruction in the diagnosis of tracheobronchial abnormalities based on three cases of children with congenital tracheobronchial strictures. Images were reconstructed using a curved planar reformat and shaded surface display. The images obtained from our three cases of tracheal stenosis, subglottic stenosis and tracheobronchial strictures were extremely clear. Spiral CT with 3D reconstruction provides excellent anatomic delineation of the tracheobronchial airway, and is safe and less invasive than tracheobronchography.

The possibility of the charge-mediated superconductivity in LiH and BeH"2 plane systems was studied by means of the Green's function method and a numerical approach. It is unlikely that the effective electron-electron interaction for these systems becomes attractive.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Conclusion Color Doppler US is a valuable diagnostic tool in evaluating or predicting prognosis of fulminant hepatic failure as it is simple and provides more accurate information about portal circulation than the other existing modalities.

The alkenyl and alkynylstannanes (I) are coupled with the perfluoroalkyl iodides (II) in the presence of a Pd(0) catalyst, producing the fluorohydrocarbons (III).

The 1,5‐dibromopentanes (I) with electron withdrawing substituents are treated with silver nitrate to form the tetrahydropyranes (II).

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reaction of phenyl azide (I) with the aromatic compounds (II) in the presence of AlCl3gives the diarylamines (III) and (IV); in some cases small amounts of other by‐products are detected.

In the presence of a mixture of TFA and CF3SO3H the reaction between phenyl azide (I) and the dialkyl sulfides (II) affords the o‐aminophenyl sulfides (IV) along with the p‐aminophenyl sulfides (V).