A quantum chemical study on the polycondensation reaction of polyesters: The mechanism of catalysis in the polycondensation reaction

We carried out a theoretical study on the mechanism of catalysis in the poly(ethylene terephthalate) (PET) polycondensation reaction. Transesterification reaction of diethylterephthalate with ethanol is investigated as a model system by using the B3LYP level of theory, and Sb(OEt)₃, Ge(OEt)₄ and Ti(OEt)₄ are adopted as model catalysts. We found that the metal center of metal alkoxides coordinates to the carbonyl oxygen atom of the ester, and the alkoxy oxygen atom of alkoxy ligands attacks to the carbonyl carbon atom of the ester to form the four-centered transition state. The activation energy for tetraethoxy titanium catalyzed reaction in vacuo is 15.47 kcal/mol; this is comparable to the experimental result of 11.2 kcal/mol for poly(butylene terephthalate)/Ti(OBu)₄. Because the other mechanisms gave much higher activation energies, this is the most convincing mechanism of PET polycondensation catalysis by antimony, germanium and titanium alkoxides.     

Surface-collection efficiency of Nuclepore filters for nanoparticles

The flat surface of Nuclepore filters is suitable for observing collected particles with a scanning electron microscope (SEM). However, experimental data on surface-collection efficiency are limited because surface-collection efficiencies cannot be measured directly using aerosol measuring instruments. In this study, the surface-collection efficiencies of Nuclepore filters were determined by establishing the ratio of the number of particles deposited on the surface of the filter visually counted with an SEM to the number of inflow particles counted by a condensation particle counter, using monodispersed polystyrene latex particles (30–800 nm) and silver particles (15–30 nm). Because Nuclepore filters with smaller pore sizes would be expected to produce higher minimum surface-collection efficiency and a higher pressure-drop, 0.08 and 0.2 µm Nuclepore filters were chosen as the test filters in view of both collection efficiency and pressure drop. The results showed that the minimum surface-collection efficiencies of the 0.08 µm pores at face velocities of 1.9 and 8.4 cm·s^?1 were approximately 0.6 and 0.7, respectively, and those of the 0.2 µm pores at face velocities of 1.5 and 8.6 cm·s^?1 were approximately 0.8 and 0.6, respectively. Because the pressure drop of the 0.2 µm pore filter was lower than that of the 0.08 µm pore filter under the same flow-rate conditions, the 0.2 µm pore filter would be more suitable considering the pressure drop and collection efficiency. The obtained surface collection efficiencies were quantitatively inconsistent with theoretical surface-collection efficiencies calculated using conventional theoretical models developed to determine the collection efficiency of filters with larger pores.

© 2016 American Association for Aerosol Research     

In utero exposure to a low concentration of diesel exhaust affects spontaneous locomotor activity and monoaminergic system in male mice

Background

Epidemiological studies suggest that inhalation of carbonaceous particulate matter from biomass combustion increases susceptibility to bacterial pneumonia. In vitro studies report that phagocytosis of carbon black by alveolar macrophages (AM) impairs killing of Streptococcus pneumoniae. We have previously reported high levels of black carbon in AM from biomass smoke-exposed children and adults. We therefore aimed to use a mouse model to test the hypothesis that high levels of carbon loading of AM in vivo increases susceptibility to pneumococcal pneumonia.

Methods

Female outbred mice were treated with either intranasal phosphate buffered saline (PBS) or ultrafine carbon black (UF-CB in PBS; 500 μg on day 1 and day 4), and then infected with S. pneumoniae strain D39 on day 5. Survival was assessed over 72 h. The effect of UF-CB on AM carbon loading, airway inflammation, and a urinary marker of pulmonary oxidative stress was assessed in uninfected animals.

Results

Instillation of UF-CB in mice resulted a pattern of AM carbon loading similar to that of biomass-smoke exposed humans. In uninfected animals, UF-CB treated animals had increased urinary 8-oxodG (P = 0.055), and an increased airway neutrophil differential count (P < 0.01). All PBS-treated mice died within 72 h after infection with S. pneumoniae, whereas morbidity and mortality after infection was reduced in UF-CB treated animals (median survival 48 h vs. 30 h, P < 0.001). At 24 hr post-infection, UF-CB treated mice had lower lung and the blood S. pneumoniae colony forming unit counts, and lower airway levels of keratinocyte-derived chemokine/growth-related oncogene (KC/GRO), and interferon gamma.

Conclusion

Acute high level loading of AM with ultrafine carbon black particles per se does not increase the susceptibility of mice to pneumococcal infection in vivo.     

Characterization of the ybdT gene product of Bacillus subtilis: Novel fatty acid β-hydroxylating cytochrome P450

We have characterized the gene encoding fatty acid α-hydroxylase, a cytochrome P450 (P450) enzyme, from Sphingomonas paucimobilis. A database homology search indicated that the deduced amino acid sequence of this gene product was 44% identical to that of the ybdT gene product that is a 48 kDa protein of unknown function from Bacillus subtilis. In this study, we cloned the ybdT gene and characterized this gene product using a recombinant enzyme to clarify function of the ybdT gene product. The carbon monoxide difference spectrum of the recombinant enzyme showed the characteristic one of P450. In the presence of H₂O₂, the recombinant ybdT gene product hydroxylated myristic acid to produce β-hydroxyristic acid and α-hydroxymyristic acid which were determined by high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry. The amount of these products increased with increasing reaction period and amount of H₂O₂ in the reaction mixture. The amount of β-hydroxyl product was slightly higher than that of α-hydroxyl product at all times during the reaction. However, no reaction products were detected at any time or at any concentration of H₂O₂ when heat-inactivated enzyme was used. HPLC analysis with a chiral column showed that the β-hydroxyl product was nearly enantiomerically pure R-form. These results suggest that this P450 enzyme is involved in a novel biosynthesis of β-hydroxy fatty acid.     

防冻型黏土质可塑料的研制

为了提高可塑料的抗冻结能力,以粒度为6～3、3～1、≤1 mm的焦宝石(w(Al2O3)>45%,w(SiO2)<52%)和粒度≤45μm的黏土(w(Al2O3)>26%,w(SiO2)<65%)为原料,加入硫酸铝溶液、水和乙二醇防冻液制备出防冻型黏土质可塑料.将试样放入零下15℃的试验箱中冷冻,在室温下放置至室温,再经110℃干燥和1 000℃热处理后,分别测试试样的线变化率、抗折强度、耐压强度和体积密度,并与常温20℃下放置的试样的各项性能加以比较.结果表明:试样经过110℃和1 000℃热处理后,普通可塑料试样在零下15℃冻结后的强度比正常未冻结试样的下降约20%,而防冻型可塑料与正常试样相比,在强度方面几乎没有改变.     

Catalytic reforming of natural gas for hydrogen production in a pilot fluidized-bed membrane reactor: Mapping of operating and feed conditions

A fluidized-bed membrane reformer was operated in two independent laboratories to map various operating conditions, to investigate the effects of changing the composition of the natural gas feed stream and to verify earlier experimental trials. Two feed natural gases were tested, containing either 95.5 or 90.1 mol% of methane (3.6 or 9.9 mol% of other gaseous higher hydrocarbons). Experimental tests investigated the influence of total membrane area, reactor pressure, permeate pressure and natural gas feed rates. A permeate-H₂-to reactor natural gas feed molar ratio >2.3 was achieved with six two-sided membrane panels under steam reforming conditions and a pressure differential across the membranes of 785 kPa. The total cumulative reforming time reached 395 h, while hydrogen purity exceeded 99.99% during all tests.     

Autoantibodies detectable in the sera of silicosis patients. The relationship between the anti-topoisomerase I antibody response and HLA-DQB1*0402 allele in Japanese silicosis patients

Eighty-one Japanese silicosis patients and 66 healthy volunteers were analyzed for autoantibodies by ELISA, and HLA-genotyping using the PCR-RFLP method was performed. Anti-topoisomerase I (anti-topo I) autoantibodies were detected in seven patients without any clinical features of autoimmune diseases such as progressive systemic sclerosis (PSS), although anti-topo I have been mostly reported in PSS patients. Antibodies directed to RNP, ssDNA, dsDNA and cent-B were not detected among the anti-topo I positive patients. The indirect immunofluorescent staining pattern of Hep-2 cells with the sera of anti-topo I positive silicosis patients demonstrated the typical mode of anti-topo I autoantibodies observed in the patients with PSS. The allelic frequency of HLA-DQB1*0402 was significantly higher in anti-topo I positive patients (28.6%) than in anti-topo I negative patients (1.5%, P < 0.001) or healthy controls (0.8%, P<0.001). HLA-DQB1*0301, DQB1*0601 and DPB1*1801 alleles were more frequently detected in anti-topo I positive patients than in the patients without anti-topo I or in healthy volunteers, but no significant difference was observed. DQB1 allele is associated with the induction of anti-topo I autoantibodies in Japanese silicosis patients, but the allele is not the same as in Caucasian PSS patients. Another allele (DQB1*0402) plays an important role in Japanese silicosis patients. The most important factor to induce anti-topo I autoantibodies seems not to be the type of alleles themselves, but the position of some specific amino acid residues in the DQ beta first domain. These findings will be useful for preventing occupational autoimmune diseases.     

Effects of polar groups of polymer matrix on reinforcement-matrix interaction in kevlar fiber-reinforced composites

In order to investigate the interaction between the polar groups of reinforcement and matrix in polymer composite, mechanical properties were studied for the Kevlar fiber-reinforced composites (Kevlar is a registered trademark of E. I. duPont de Nemours Co. Inc.), in which the kind and fraction of polar components in matrix were varied using blended polymers. For the composites comprised of polymethyl methacrylate and poly(hydroxypropyl ether of bisphenol A) as the matrix, a subtransition, which can be ascribed to the interphase formed on the reinforcement surface by a strong interaction between reinforcement and matrix, appears at a temperature above the primary transition on the E″ versus temperature curves. Such a subtransition is obscured or diminished accompanying the decrease in fraction of the polar components in the matrix. The fiber efficiency factors for strength are also decreased with a decrease in the fraction of the polar components. These results imply that the reinforcement-matrix interaction is affected depending on the fraction of the polar components in matrix. For the composite comprised of blending the two polar components as the matrix, each component can contribute to the interaction with the reinforcement. The results obtained from the Fourier transform infrared spectroscopy on the matrix polymer-coated Kevlar cloth do not contradict those obtained by studying the mechanical properties.     

The development of MHD cold wall channels in the oil-fired condition

The durability of a cold wall MHD generator consisting of metal electrodes and alumina-coated peg insulators was experimentally examined in the oil-fired MHD condition with the additive of SO₂ corresponding to S = 0.54 wt%. The structure of the electrode wall and various anode and cathode materials were tested, with particular reference to developing long-life electrodes. It was clarified that Pt, SHOMAC (28.8 Cr−1.9 Mo) and SUS-304 as anodes and W---Cu (70 W−30 Cu) and WC---Ag (60 WC−40 Ag) alloys as cathodes were promising for durability and that the structure of an anode divided into two elements connected to each other with an SnO₂ resistor was very useful for uniformity of the anode corrosion pattern and the inter-anode voltages. It is reasonable to expect, from the test results, that the lifetime of a cold wall MHD generator in an oil-fired commercial plant will be over 4000 h, and therefore, a foundation for its commercial use has been established.     

Fundamental Evaluation of Power Supply and Rectifiers for Wireless Power Transfer Using Magnetic Resonant Coupling

This paper provides a fundamental analysis of a power supply and rectifiers for wireless power transfer using magnetic resonant coupling (MRC). MRC enables efficient wireless power transfer over middle‐range transfer distances. MRC for wireless power transfer should operate at a high frequency in the industry science medical band, such as 13.56 MHz, because the size of the transfer device decreases at higher transfer frequencies. Therefore, the output frequency of the power supply on the transmitting side should be 13.56 MHz. In addition, the rectifier on the receiving side is operated at a high frequency. This paper focuses on the reflected power in the power supply and rectifiers. Thus, the parametric design method is clarified for the power supply, including a low‐pass filter to match the output, the impedance of the power supply with the characteristic impedance of the transmission line. In addition, the effects on the rectifiers of silicon carbide and gallium nitride diodes are confirmed by performing an experiment and a loss analysis.