Measurement of internal stresses in coatings using time resolved fluorescence

This paper describes a new nondestructive technique for detecting internal stresses in coatings using time resolved fluorescence. The measurement principle is based upon an experimental result that the decay time of fluorescence from poly(3-octylthiophene), P3OT, dispersed in uniaxially-stretched polymer films decreases with increasing tensile stress acting on the films. Internal stresses in the clear coat and in the base coat of a multilayer structure, which was composed of electrodeposited coat, surface coat, base coat, and clear coat, were estimated from the decay time of fluorescence from P3OT in both coats. The order of internal stresses in the clear coat and base coat of the multilayer system was 1 MPa. When the coatings were piled up, the internal stress decreased as the distance from a metal substrate was increased. It was found that moisture and temperature influenced internal stresses in the clear coat rather than in the base coat. Internal stress in the clear coat, which was one layer coated on a metal substrate, was measured by the traditional bimetallic method or by the time resolved fluorescence technique. Comparing both methods, it was concluded that the time resolved fluorescence technique gave reliable values for internal stresses in coatings.     

Measurement of residual stresses in injection‐molded polymer parts by time‐resolved fluorescence

Time‐resolved fluorescence properties of 9‐methylanthracene (9MAn) dispersed in film of polyvinylchloride (PVC) containing carbon black were studied under tensile loadings. The fluorescence lifetime of 9MAn decreased from 5.70 to 5.55 ns, whereas the stresses acting on the films increased from 0 to 3 MPa. The change in fluorescence lifetimes of 9MAn during the stress relaxation process showed that the fluorescence lifetimes were correlated with the stresses, not with the strains. The results suggest that 9MAn is a useful probe for monitoring stresses acting on the matrix. With the use of the fluorescence properties of 9MAn, the residual tensile stresses on the skin‐layer of PVC injection‐molded test pieces were estimated. The estimated residual stresses were about ～ 1 MPa. The residual stresses were relaxed to 0 MPa with annealing at 100°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2600–2603, 2002     

Bending of ionic polymer gel caused by swelling under sinusoidally varying electric fields

Deformation of poly(vinyl alcohol)–poly(sodium acrylate) composite hydrogel (PVA–PAA gel) under sinusoidally varying electric fields was studied in electrolyte solutions. The PVA–PAA gel was prepared by repeatedly freezing and thawing a mixed solution of PVA and polyacrylic acid. A cyclic bending–straightening motion of the PVA–PAA gel rods of about 1 mm in diameter have been observed in Na₂CO₃ aqueous solutions under the fields. The PVA–PAA gel had a response time of less than several hundreds milliseconds. The bending has also been observed in organic solvents containing an electrolyte when the organic solvent is electrolyzed. It was found that the motion of the gel under electric fields of less than 1 Hz occurred mainly through swelling due to the change of the osmotic pressure based upon the difference of the ion concentration. However, it has not been determined whether the motion at higher frequencies is caused by the osmotic effect. © 1993 John Wiley & Sons, Inc.     

Technique for anisotropic extension of organic crystals: application to temperature dependence of electrical resistance

We have developed a technique for the anisotropic extension of fragile molecular crystals. The pressure medium and the instrument, which extends the pressure medium, are both made from epoxy resin. Since the thermal contraction of our instrument is identical to that of the pressure medium, the strain applied to the pressure medium has no temperature dependence down to 2 K. Therefore, the degree of extension applied to the single crystal at low temperatures is uniquely determined from the degree of extension in the pressure medium and thermal contractions of the epoxy resin and the single crystal at ambient pressure. Using this novel instrument, we have measured the temperature dependence of the electrical resistance of metallic, superconducting, and insulating materials. The experimental results are discussed from the viewpoint of the extension (compression) of the lattice constants along the parallel (perpendicular) direction.     

DNA‐Templated Synthesis of Perylenediimide Stacks Utilizing Abasic Sites as Binding Pockets and Reactive Sites

DNA is considered to be a promising biomolecule as a template and scaffold for arranging and organizing functional molecules on the nanoscale. The construction and evaluation of DNAs containing multiple functional molecules that are useful for optoelectronic devices and sensors has been studied. In this paper we report the efficient incorporation of perylenediimide (PDI) units into DNA by using abasic sites both as binding sites and as reactive sites and the construction of PDI stacks within the DNA structure, accomplished through the preorganization of the PDI units in the hydrophobic pocket within the DNA. Our approach could become a valuable method for construction of DNA/chromophore hybrid structures potentially useful for the design of DNA‐based devices and biosensors.     

An immuno-wall microdevice exhibits rapid and sensitive detection of IDH1-R132H mutation specific to grade II and III gliomas

World Health Organization grade II and III gliomas most frequently occur in the central nervous system (CNS) in adults. Gliomas are not circumscribed; tumor edges are irregular and consist of tumor cells, normal brain tissue, and hyperplastic reactive glial cells. Therefore, the tumors are not fully resectable, resulting in recurrence, malignant progression, and eventual death. Approximately 69–80% of grade II and III gliomas harbor mutations in the isocitrate dehydrogenase 1 gene (IDH1), of which 83–90% are found to be the IDH1-R132H mutation. Detection of the IDH1-R132H mutation should help in the differential diagnosis of grade II and III gliomas from other types of CNS tumors and help determine the boundary between the tumor and normal brain tissue. In this study, we established a highly sensitive antibody-based device, referred to as the immuno-wall, to detect the IDH1-R132H mutation in gliomas. The immuno-wall causes an immunoreaction in microchannels fabricated using a photo-polymerizing polymer. This microdevice enables the analysis of the IDH1 status with a small sample within 15 min with substantially high sensitivity. Our results suggested that 10% content of the IDH1-R132H mutation in a sample of 0.33 μl volume, with 500 ng protein, or from 500 cells is theoretically sufficient for the analysis. The immuno-wall device will enable the rapid and highly sensitive detection of the IDH1-R132H mutation in routine clinical practice.     

Mechanism‐Based Trapping of the Quinonoid Intermediate by Using the K276R Mutant of PLP‐Dependent 3‐Aminobenzoate Synthase PctV in the Biosynthesis of Pactamycin

Mutational analysis of the pyridoxal 5′‐phosphate (PLP)‐dependent enzyme PctV was carried out to elucidate the multi‐step reaction mechanism for the formation of 3‐aminobenzoate (3‐ABA) from 3‐dehydroshikimate (3‐DSA). Introduction of mutation K276R led to the accumulation of a quinonoid intermediate with an absorption maximum at 580 nm after the reaction of pyridoxamine 5′‐phosphate (PMP) with 3‐DSA. The chemical structure of this intermediate was supported by X‐ray crystallographic analysis of the complex formed between the K276R mutant and the quinonoid intermediate. These results clearly show that a quinonoid intermediate is involved in the formation of 3‐ABA. They also indicate that Lys276 (in the active site of PctV) plays multiple roles, including acid/base catalysis during the dehydration reaction of the quinonoid intermediate.     

Disorders and oxygen vacancies in p-type Sn2B2O7 (B = Nb,Ta): Role of the B-site element

Sn₂Nb_2−xTa_xO₇ (x = 0.0–2.0) with pyrochlore structure is a promising material for p-type oxide semiconductors. A systematic study of its Nb/Ta ratio indicated that the hole–generation efficiency of the Nb end (Sn₂Nb₂O₇) was an order of magnitude lower than that of the Ta end (Sn₂Ta₂O₇). Although this occurs due to differences in oxygen-vacancy formation, the origins of the hole–generation efficiencies remain unclear due to limited information on local and global crystal-structure disorders in pyrochlore Sn₂Nb₂O₇ and Sn₂Ta₂O₇. In this study, the crystal structures of Sn₂B₂O₇ (B = Nb, Ta), composed of BO₆ octahedra and Sn₄O tetrahedra, were investigated using X-ray absorption spectroscopy and X-ray diffraction. A detailed investigation of the local and global crystal structures indicated a larger amount of disorder in the Sn₄O tetrahedra in Sn₂Nb₂O₇ compared to Sn₂Ta₂O₇; disorder in the BO₆ octahedra occurred only in Sn₂Ta₂O₇. This study indicates that an appropriate selection of the B-site element is vital for suppressing defect and disorder formation in Sn₄O tetrahedra and subsequently improving the hole–carrier–generation efficiency.     

Fluorescence EXAFS analysis of ErP grown on InP by organometallic vapor phase epitaxy using a new organometal Er(EtCp)3

We have investigated local structures of ErP grown by organometallic vapor phase epitaxy Er source: tris(ethylcyclopentadienyl)erbium (Er(EtCp)₃ by extended X-ray absorption fine structure (EXAFS) measurement. The EXAFS analysis revealed that NaCl-type ErP and Er–O(–C) compounds coexisted in the case of ErP growth by using Er(EtCp)₃. The NaCl-type ErP was preferentially formed on InP(1 1 1)A compared with InP(0 0 1) and InP(1 1 1)B. It is considered that formation of unexpected Er–O(–C) compounds is due to low but significant concentration of residual O and/or C in Er(EtCp)₃.