Site‐Selective Iron(III) Chloride‐Catalyzed Arylation of 4‐Aryl‐4‐methoxy‐2,5‐cyclohexadienones for the Synthesis of Polyarylated Phenols

The iron(III) chloride‐catalyzed Friedel–Crafts arylation of 4‐aryl‐4‐methoxy‐2,5‐cyclohexadienones, which were easily prepared by the phenyliodine(III) diacetate (PIDA)‐mediated oxidation of 4‐arylphenols in methanol, proceeded site‐selectively to form meta‐terphenyl (2,4‐diarylphenol) derivatives in good yields. The subsequent PIDA‐mediated oxidation and iron(III) chloride‐catalyzed Friedel–Crafts arylation of the resulting products gave the corresponding 2,4,6‐triarylphenol derivatives. The present method provides useful highly substituted polyarylated compounds.

     

燃烧合成AlN粉体的放电等离子烧结及其导热性能

利用放电等离子烧结(spark plasma sintering,SPS)工艺研究了燃烧合成法制备的2种具有不同形貌的AlN粉以及1种碳热还原氮化法制备的市售亚微米级AlN粉的烧结性能、致密化机理以及导热性能。结果表明:燃烧合成法制备的AlN纳米晶须状粉末具有与亚微米级标准市售AlN粉末同样优异的烧结性能,都能够在无烧结助剂情况下在1600℃的较低温度下烧结致密。在烧结过程中,由于燃烧合成AlN粉自身的高化学活性和SPS产生的等离子体活化作用,使得AlN粉以自身的分解-再结晶-凝聚机制进行致密化,导致晶界强度很高,断裂时以穿晶断裂为主;而在市售AlN粉末烧结过程中以表面扩散机制致密化,在晶界处形成了AlON相,降低了晶界强度,因此以沿晶断裂为主。AlN原料的氧含量对热导率的影响很大。由于燃烧合成AlN粉体的氧含量较碳热还原法制备的市售AlN粉体略高,导致其烧结试样热导率略低。     

Development of a strain for efficient degradation of polychlorinated biphenyls by patchwork assembly of degradation pathways

Rhodococcus jostii RHA1 accumulates chlorobenzoates (CBA) during the degradation of polychlorinated biphenyls (PCBs). CBA degradation is considered one of the rate-limiting steps in the complete degradation of PCBs. To reduce the accumulation of CBAs, the upper pathway enzyme genes for PCB degradation of RHA1 were introduced into a CBA-degrading bacterium, Burkholderia sp. NK8. The resulting recombinant strain exhibited no biphenyl 2,3-dioxygenase (BphA) activity encoded by bphAaAbAcAd genes, which encode the large and small subunits of the terminal oxygenase component and the ferredoxin and reductase subunits responsible for electron transfer from NADH to the large subunit. The remaining enzyme genes involved in the transformation of biphenyl to benzoate, bphB2C1D1, which encode dehydrogenase, ring-cleavage dioxygenase and hydrolase, conferred activities to NK8. To obtain the BphA activity of RHA1 in NK8, sets of BphA genes were constructed by combining the bphAaAbAcAd genes of RHA1 and bphA3A4 of Pseudomonas pseudoalcaligenes KF707, encoding the ferredoxin and reductase subunits. Hybrid derivatives of BphA containing the KF707 bphA3 conferred BphA activity to NK8, and a derivative containing the RHA1 bphAaAb and KF707 bphA3A4 genes exhibited the highest BphA activity. A plasmid containing the RHA1 bphAaAb and KF707 bphA3A4 genes plus the RHA1 bphB2C1D1 genes was constructed and introduced into NK8. The resulting recombinant strain efficiently degraded 2-, 3- and 4-chlorobiphenyls with an apparent reduction in CBA accumulation in comparison to the recombinant mutant strain, which had an insertion in the cbeA gene to inactivate CBA dioxygenase.     

Monte Carlo simulation of diffusive-to-ballistic transition in phonon transport

Heat conduction properties in Si nanostructures are analyzed using a Monte Carlo method developed for solving the phonon Boltzmann transport equation. The thermal resistances are evaluated for the systems with various sizes, and the transition from the diffusive to the ballistic heat conduction are investigated. We compare the two different phonon dispersion models (the realistic dispersion relation based on the adiabatic bond charge model and the analytically approximated model), and it is shown that the correct implementation of the phonon dispersion relation is essential to accurately simulate the quasi-ballistic heat conduction properties, which becomes obvious in the structures smaller than the phonon mean free path.     

Structural Investigation of 95(0.6Li2S0.4SiS2)5Li4SiO4 Oxysulfide Glass by Using X-ray Photoelectron Spectroscopy

S2 p and O1 s photoelectron spectra were obtained for the 95(0.6Li₂S0.4SiS₂)5Li₄SiO₄ oxysulfide glass prepared by twin-roller quenching. A four-peak deconvolution technique was used to separate the S2 p peak of the glass into the components of bridging and nonbridging sulfur atoms. As a result of the deconvolution of the S2 p peak, we found that ∼92% of the sulfur atoms were present as nonbridging atoms. The O1 s peak of the glass was separated into two components: bridging and nonbridging oxygen atoms. This separation of the O1 s peak indicated that ∼85% of the oxygen atoms were present as bridging oxygen atoms.     

Utilization of a Biodegradable Mulch Sheet Produced from Poly(Lactic Acid)/Ecoflex?/Modified Starch in Mandarin Orange Groves

We have developed a mulch sheet made by inflation molding of PLA, Ecoflex^® and modified starch, which all have different biodegradabilities. A field test of use as an agricultural mulch sheet for mandarin oranges was carried out over two years. The mechanical properties of the mulch sheet were weakened with time during the field test, but the quality of the mandarin oranges increased, a result of the controlled degradation of the sheet. The most degradable modified starch degraded first, allowing control of the moisture on the soil. Accelerator mass spectroscopy was used for evaluation of the biomass carbon ratio. The biomass carbon ratio decreased by degradation of the biobased materials, PLA and modified starch in the mulch sheet.     

Cooperative localization by using knowledge of self-organized regularity

In this article, a new localization approach for a team of robots that use the emergent properties of their formation is proposed. Synchronized behavior sometimes generates spin-off effects that include geometric patterns. The question then arises as to whether it is possible to use these patterns for something important for robots. In this article, Takayama’s control strategy, which is a target enclosure formation, is discussed. A simple and useful expansion of Monte Carlo localization by the emergent pattern is proposed. The proposed algorithms are confirmed through a series of computer simulations.     

Thermal cis–trans conversion in thiophene oligomers

Thermal cis–trans conversion has been examined in oligothiophene single molecules encapsulated in the molecular vessels of cyclodextrin and Na-mordenite. At high temperatures, optical absorption intensities are enhanced in bithiophene, terthiophene and quinquethiophene, while the intensity of quarterthiophene is temperature independent. Optical absorption comes from uncompensated transition dipole moment due to the thermal torsion between cis and trans forms.     

Dawn of molecular dynamics

The early development of electronic computers and molecular dynamics is reviewed with an emphasis on the present author's work.     

Irradiation-Assisted Stress-Corrosion Cracking of Nitinol During eBeam Sterilization

Medical device fractures during gamma and electron beam (eBeam) sterilization have been reported. Two common factors in these device fractures were a constraining force and the presence of fluorinated ethylene propylene (FEP). This study investigated the effects of eBeam sterilization on constrained light-oxide nitinol wires in FEP. The goal was to recreate these fractures and determine their root cause. Superelastic nitinol wires were placed inside FEP tubes and constrained with nominal outer fiber strains of 10, 15, and 20%. These samples were then subjected to a range of eBeam sterilization doses up to 400 kGy and compared with unconstrained wires also subjected to sterilization. Fractures were observed at doses of >100 kGy. Analysis of the fracture surfaces indicated that the samples failed due to irradiation-assisted stress-corrosion cracking (IASCC). This same effect was also observed to occur with PTFE at 400 kGy. These results suggest that nitinol is susceptible to IASCC when in the presence of a constraining stress, fluorinated polymers, and irradiation.