Structural changes in isothermal crystallization process of polyoxymethylene investigated by time-resolved FTIR, SAXS and WAXS measurements

Structural evolution in the isothermal crystallization process of polyoxymethylene from the molten state has been investigated by carrying out the time-resolved measurements of infrared spectra and synchrotron small angle X-ray scattering (SAXS) and wide angle X-ray scattering. In case of isothermal crystallization at 130 °C, for example, the infrared bands intrinsic of folded chain crystal (FCC) morphology appeared at first, and then the bands of extended chain crystal (ECC) morphology were detected with time delay of ca. 150 s. In the SAXS experiment at 130 °C, the lamellar stacking structure of the long period of ca. 15 nm was observed at first, which changed rapidly to ca. 12 nm in a short time. The SAXS peak with the long period of ca. 6 nm started to appear with a time delay of ca. 150 s after the initial lamellae appeared and coexisted with the initially-observed 12 nm peak. Judging from the timing to detect these characteristic infrared and SAXS signals, a good correspondence was found to exist between the stacked lamellar structure of 12 nm long period and FCC morphology and between the structure of 6 nm long period and ECC morphology. The quantitative analysis was made for the SAXS data on the basis of the lamellar insertion model combined with the paracrystalline theory of the second-kind of disorder. The following structural evolution was deduced from all these results. Immediately after the temperature jump from the melt to 130 °C, the stacked lamellar structure of FCC morphology was generated at first. New lamellae were formed from the amorphous region in between the originally-existing lamellae about 150 s later, where the random chain segments bridging the adjacent lamellae were extended to form the taut tie chains, giving infrared bands of ECC morphology. This inserted lamellar structure of 6 nm long period coexisted at a population of ca. 6% with the initially-formed lamellar stacking structure of 12 nm long period. When the experiment was made at 150 °C, only the formation of stacked lamellar structure of FCC morphology was observed and the insertion of new lamella did not occur.     

Post-lunch nap as a worksite intervention to promote alertness on the job.

A worksite study was conducted to examine whether a 15-min nap during a post-lunch rest period would affect subsequent alertness, performance, and nocturnal sleep in eight factory workers under a 3-week protocol. Subjects were asked to take the nap at 12:30 h on a reclining chair during the nap week, and to remain awake during the no-nap week. The order of these 2 weeks was counterbalanced between the subjects. During the third, follow-up week, each subject determined whether or not she/he would nap. Alertness on the job and nocturnal sleep were assessed using a sleep diary. Wrist activity was also recorded during sleep at night. Choice reaction time task (RT) was performed at 10:00 and 15:00 h every day of the nap week and every other day of the no-nap and follow-up weeks. Perceived alertness was significantly higher in the afternoon after nap than after no nap at the end of the week. Similar effects were observed during the follow-up week where almost half of the subjects napped. No significant differences between the three weeks were found for RT performance or nocturnal sleep. Workers' attitudes toward the nap were favourable. Although further intervention research is required, our results suggest that post-lunch napping may have the potential to promote daytime alertness at work.     

Primary biliary cirrhosis: symptoms, laboratory data and diagnosis

The most frequent and important symptoms in primary biliary cirrhosis (PBC) are pruritus and jaundice. In the majority, jaundice appears within one half to two years of onset of pruritus. Xanthoma, bone change and sicca syndrome are often observed. The recent increase in number of asymptomatic PBC is the result of progagation of medical examination. In the biochemical tests, elevation of the biliary enzymes, such as ALP and gamma-GTP, is characteristic, as well as, a high level of serum IgM. Serum bilirubin values are gradually raised along with the clinical course of the disease. Positive antimitochondrial antibody (AMA) is the most valuable immunological finding for the diagnosis of PBC. Anti-pyruvate dehydrogenase complex E2 component E2 has the same significance as AMA. Diagnostic criteria si shown in this paper.     

Epstein-Barr virus-positive multiple early gastric cancers and dysplastic lesions: a case report

Epstein-Barr virus (EBV) has been implicated as a causal virus of gastric cancer with episomal monoclonality, elevated antibodies and a unique morphologic expression in the early intramucosal stage, but the infection mechanisms have not been demonstrated. EBV has been shown only in the cancerous lesions by the highly sensitive EBV-encoded small RNA in situ hybridization (EBER-ISH) method, not in the dysplastic mucosa adjacent to the cancer. A case is presented of multiple EBV-positive gastric cancer and dysplastic epithelium observed in a 52-year-old man. Serial cut sections of the gastrectomy specimen showed four small cancerous lesions, three of which were EBER-positive, and three EBER-positive, minute, non-cancerous dysplastic lesions. The three cancerous lesions were intramucosal cancer, with one having minimal submucosal invasion forming a lymphoepithelioma-like histology. All of these EBER-positive cancerous and dysplastic lesions showed intense CD8 T-lymphocytic infiltration. There was no such findings in the EBV-negative cancerous lesion. It was concluded that EBV infection may occur in the epithelial cells of atrophic gastric mucosa, and progress to cancer with monoclonal expansion through the EBV-positive dysplastic change. Cytotoxic T-lymphocytic reactions can occur even in the dysplastic lesions. Multifocal EBV infection in the gastric mucosa may occur and, if necessary, total gastrectomy is recommended in such a case.     

Molecular cloning of a novel melanocortin receptor

Using the technique of the polymerase chain reaction primed with oligonucleotides based on the homologous transmembrane regions of seven transmembrane G protein-linked receptors, we isolated three full-length human genes that encode a novel subgroup of this receptor family. Recently, two of these receptors were identified as specific for alpha-melanocyte-stimulating hormone (alpha-MSH) and adrenocorticotropic hormone. We report the molecular cloning and pharmacologic characterization of a third member of this subgroup. The gene for this receptor encodes a protein of 361 amino acids in length. Its pharmacology characterizes it as an MSH receptor specific to the heptapeptide core common to adrenocorticotropic hormone and alpha-, beta-, and gamma-MSH. By Northern blot hybridization and polymerase chain reaction, it is expressed in brain, placental, and gut tissues but not in melanoma cells or in the adrenal gland. These findings may yield insight into the physiology of peptides derived from pro-opiomelanocortin post-translational processing.     

Thallium-201 myocardial SPECT in Bland-White-Garland syndrome: two adult patients with inferoposterior perfusion defect

A myocardial 201TI SPECT examination was conducted both prior to and following surgery of two adult patients with an anomalous left coronary artery originating from the pulmonary artery (Bland-White-Garland syndrome). In this syndrome, the anterior wall is usually affected first. Preoperative examination demonstrated an inferoposterior perfusion defect. In both patients, the right coronary artery was markedly dilated, and a significant left-to-right shunt formation was observed. Both patients were diagnosed as possibly having coronary steal syndrome. A prolonged inadequate blood supply to the right coronary region may cause inferoposterior cardiomyopathy. In the postoperative examination, myocardial perfusion markedly improved in one patient whose preoperative SPECT showed redistribution in a delayed scan. Thallium-201 SPECT was therefore found to be useful in assessing both the preoperative and postoperative myocardial perfusion.     

Structural change in the Brill transition of Nylon m/n (1) Nylon 10/10 and its model compounds

Structural changes in the Brill transitions of Nylon 10/10 and its model compounds have been investigated by carrying out the temperature-dependent measurements of X-ray diffraction and infrared spectra along with the DSC measurement. The crystal structure at room temperature was found to be the so-called α form with the all-trans zigzag methylene segments. When the samples were heated, the infrared progression bands of the methylene segments, which are sensitive to the length of all-trans segmental parts, were found to change their spectral patterns in the transition temperature region: the progression bands decreased in intensity and disappeared above the transition region. At the same time several new bands were observed to appear, which were found to correspond to the progression bands of (CH₂)₇-(CH₂)₅trans-zigzag segments. These spectral changes indicate that the methylene segments were conformationally disordered by an invasion of some gauche bonds and as a result the effective length of trans-zigzag segments became shorter. This conformational disordering was found to occur more remarkably in the methylene segment of NH-(CH₂)₁₀-NH part than the CO-(CH₂)₈-CO part. At the same time the infrared bands of amide groups, in particular the bands sensitive to the twisting angles about the CH₂-amide bonds were found to show the remarkable change, indicating the local conformational change from planar-zigzag to twisted form in the CH₂-amide moiety. The frequency shift of amide A band (NH stretching mode) indicated a weakening of intermolecular hydrogen bonds, which however, did not disappear up to the melting region. From these data combined with the X-ray diffraction data, the structural disordering in the Brill transition phenomena was deduced concretely.     

Modern interpretation on the high-stretching of natural rubber attained by the classic ‘racking’ method

To investigate the mechanism of high elongation of natural rubber attained by the ‘racking method’, a strip of smoked-sheet was elongated up to 150 times in length, by stretching rapidly at room temperature and forcing to shrink at 75-80 °C repeatedly. On X-ray diffraction, a typical fibre pattern with an amorphous ring appeared already at ×10 (stretch ratio=10). The degree of crystallinity increased to the level of 17-18% at ×20 and turned to decrease after ×60, but the degree of crystallite orientation reached at a high level already at ×10 and did not change significantly and the half-height width of reflection profiles stayed almost at a constant level, while the Young's modulus increased up to ca. 300 MPa at ×100 and then fell rather discontinuously. It was assumed that some fractions of chain segments between entanglements were gradually broken in each step of stretching operation, rather than disentangled and slipped.     

Influence of third monomer on the crystal phase transition behavior of ethylene-tetrafluoroethylene copolymer

Crystal phase transition between the low- and high-temperature phases has been investigated for ethylene (E)-tetrafluoroethylene (TFE) alternating copolymer (ETFE) containing the third monomeric species by the temperature dependent measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) and differential scanning calorimetry. Nonafluoro-1-hexene (NFH) and hexafluoropropylene (HFP) were chosen as the third monomers, where they are different in the side-branch length, -(CF₂)₃CF₃ and -CF₃, respectively. In the case of E/TFE/NFH copolymer (ET-C4F9), the crystal phase transition temperature of the original ETFE two-components copolymer was not very much affected by the existence of NFH in the range of NFH content from 0.7 to 3 mol%. Contrarily, the crystal phase transition temperature of E/TFE/HFP copolymer (ET-CF3) was found to decrease drastically with increasing HFP content. The melting temperature and the higher-order structure were also affected sensitively depending on the HFP content. This difference in phase transition behavior between ET-C4F9 and ET-CF3 copolymers is reasonably interpreted as follows: the short side groups (-CF₃) of HFP monomeric unit are included in the crystal lattice of E/TFE chains and the unit cell is expanded gradually with an increment of the HFP content, resulting in the decrease in phase transition point because of easier thermal motion of the chains. On the other hand, the long side groups [-(CF₂)₃CF₃] of NFH monomeric units are excluded out of the crystal lattice and located on the lamellar surfaces or in the amorphous region and do not affect very much the phase transition temperature even when the NFH content is increased. In association with such a change in crystal structure, the long period of stacked lamellar structure was found to decrease remarkably in the case of NFH, whereas it does not change very much for HFP, consistent with the interpretation of the above-mentioned WAXD data.