Carbon radicals generated by solid polymers: Electron spin resonance spectroscopy for detection of species in water

Radicals generated in plastic medical devices (solid phase) by γ-rays or electron-beam irradiation during sterilization are known to cause oxidation of protein drugs, resulting in a loss or reduction in drug efficacy. The generation of radical species in water by the radical species in solid polymers has not been proved. Using electron spin resonance (ESR) spectroscopy, we confirm the generation of new radicals in water by γ-ray irradiated cyclic olefin polymers (COP). ESR measurements are obtained using 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL) as a spin probe and 5-(2,2-dimethyl-1,3-propoxycyclophosphoryl)-5-methyl-1-pyrroline N-oxide (CYPMPO) as a spin trap, in which the irradiated COP was immersed. The ESR signals indicate the TEMPOL radicals decline over time, suggesting the generation of new radicals. Conversely, the characteristic ESR signals of the adduct formed by the reaction between CYPMPO and the hydroxyl radical are observed. Thus, hydroxyl radicals are generated because of the migration of the radicals from COP to water. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48604.     

Applicability of GC, GC/MS and liquid chromatography with tandem mass spectrometry to screening for 140 pesticides in agricultural products

The applicability of GC, GC/MS and liquid chromatography with tandem mass spectrometry (LC/MS/MS) to screening for 140 pesticides in agricultural products was examined. Validation of multi-residue screening methods for the determination of 88 pesticides in 12 crops (asparagus, cauliflower, burdock, carrot, broccoli, spinach, matsutake mushroom, orange, soybean, sesame, millet and tea) was done by GC and GC/MS. Of the 88 pesticides, 63 were obtained with recoveries in the range from 50 to 150% at the 0.1 microg/g level in the 12 crops. Applicability of the official methods in Japan to 74 pesticides, including 22 pesticides with low recovery (< 50%) by GC or GC/MS analysis, was also examined by LC/MS/MS. LC/MS/MS acquisition parameters were established for 67 pesticides in positive and negative electrospray ionization (ESI) modes. Of 67 pesticides validated in 7 crops using LC/MS/MS at the 0.1 microg/g level, 44 showed recoveries in the range from 50 to 150%. The occurrence of matrix interference in LC/MS/MS can lead to false-positive detection of MCPA in spinach, cabbage and orange and false-negative detection of four pesticides in orange, spinach, apple and unpolished rice. Good linearity was observed in the studied ranges by GC, GC/MS (r > 0.990) and LC/MS/MS (r > 0.995). Of the total of 140 pesticides validated by GC, GC/MS and LC/MS/MS, 107 were newly recognized as suitable subjects for screening.     

Measurement of aluminum or silicon activity in Fe-Ni (< 30 %) alloys using mullite and ZrO2-based solid electrolyte galvanic cell

Using mullite (3Al₂O₃·2SiO₂)-tube type and ZrO₂ (MgO mole fractions of 9 %)-plug type solid electrolyte, the activities of Al in the Fe-15, 29% Ni-0.002 to 0.84% Al (mass contents in%) alloys were measured at 1873 K in an Al₂O₃ crucible, and those of Si in the Fe-13, 28% Ni-0.13 to 2.3% Si alloys were measured at 1823 K in a mullite crucible with an excess of SiO₂. The interaction coefficients of and were determined as ?0.0173 ± 0.0052 and 0.00021 ± 0.00007, respectively, and those of and were determined as 0.0094 ± 0.0049 and ?0.00008 ± 0.00004, respectively. The oxygen activities obtained by the EMF measurements were compared with those obtained from the contents of analyzed oxygen. The oxygen activities in the Fe-Ni-Al alloys were found to be supersaturated. The interaction coefficients of and were determined as 0.0027 ± 0.0012 and 0.00012 ± 0.00004, respectively, from the contents of analyzed oxygen in Fe-Ni-Si alloys.     

Galvanic cell measurements on supersaturated activities of oxygen in Fe-Al-M (M=C, Te, Mn, Cr, Si, Ti, Zr, and Ce) melts

Using a mullite (3Al₂O₃ · 2SiO₂)-tube and ZrO₂-9 mol pct MgO-plug type solid electrolyte galvanic cells, the activities of supersaturated oxygen in Fe-0.0017 to 0.41 mass pct Al-M (M=C, Te, Mn, Cr, Si, Ti, Zr, and Ce) alloys were measured as a function of total Al or M contents at 1873 K in an alumina crucible. Based on these results, the effects of alloying elements on the supersaturated oxygen activity with respect to alumina precipitation were studied. In the Fe-Al-M (M=C, Te, Mn, Cr, and Si) alloys, the supersaturated oxygen activities for a given Al level approach the equilibrium values with increasing contents of alloying elements. However, the oxygen activities for a given Al level are still supersaturated in the Fe-Al-M (M=Ti, Zr, and Ce) alloys even in the presence of considerable amounts of the alloying elements.     

Intramolecular triplet energy migration in poly(2-vinylnaphthalene) and poly(naphthylalkyl methacrylate)s in solid solution: Effects of side chain length

Summary The effect of side chain length on intramolecular triplet energy migration of naphthalene containing polymers was investigated by a delayed fluorescence (DF) spectroscopy for the solid solution of the polymers. The degree of triplet energy migration depends strongly on whether the chromophores are directly attached to the main chain or not.     

Correlations of Hepatic Hemodynamics,Liver Function,and Fibrosis Markers in Nonalcoholic Fatty Liver Disease: Comparison with Chronic Hepatitis Related to Hepatitis C Virus

The progression of chronic liver disease differs by etiology. The aim of this study was to elucidate the difference in disease progression between chronic hepatitis C (CHC) and nonalcoholic fatty liver disease (NAFLD) by means of fibrosis markers, liver function, and hepatic tissue blood flow (TBF). Xenon computed tomography (Xe-CT) was performed in 139 patients with NAFLD and 152 patients with CHC (including liver cirrhosis (LC)). The cutoff values for fibrosis markers were compared between NAFLD and CHC, and correlations between hepatic TBF and liver function tests were examined at each fibrosis stage. The cutoff values for detection of the advanced fibrosis stage were lower in NAFLD than in CHC. Although portal venous TBF (PVTBF) correlated with liver function tests, PVTBF in initial LC caused by nonalcoholic steatohepatitis (NASH-LC) was significantly lower than that in hepatitis C virus (C-LC) (p = 0.014). Conversely, the liver function tests in NASH-LC were higher than those in C-LC (p < 0.05). It is important to recognize the difference between NAFLD and CHC. We concluded that changes in hepatic blood flow occurred during the earliest stage of hepatic fibrosis in patients with NAFLD; therefore, patients with NAFLD need to be followed carefully.     

Mechanical and physical characteristics of cellulose‐fiber‐filled polyacetal composites

We investigated the mechanical and physical characteristics of composites composed of polyacetal [alternatively called polyoxymethylene (POM)] and cellulose fiber (CelF) derived from wood pulp [10–52 wt % (9.3–50.1 vol %)] without any fiber surface treatment. The modulus, deflection temperature under load, and thermal conduction coefficient of the POM/CelF composites were effectively enhanced with increasing CelF content, and the composites had an advantage of specific modulus compared to glass fiber (GF)‐filled POM. The flexural modulus of POM/CelF 40 wt % (38.2 vol %) was measured to be about 6 GPa, which was comparable to that of POM/GF 20 wt % (12.1 vol %). In the composites, the CelFs were distributed randomly as monofilaments, and the debonding of the interface between the fibers and POM matrices in the fracture faces was confirmed as less by scanning electron microscopy observation. The POM/CelF composites possessed lower specific wear rates than the POM/GF composites, and they had damping behaviors near that of neat POM. No clear dependence of the melt flow index of the base POM on these characteristics was observed, except on Charpy impact strength. The composites studied here were unique in their performance and ability to be designed in accordance with specific demands, and they could be potential replacements for mineral‐filled and GF‐filled POM composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010