Biodegradable Polymeric Materials—Not the Origin but the Chemical Structure Determines Biodegradability

It is completely plausible that unmodified materials of natural origin, such as the native macromolecules cellulose or starch, are biodegradable. If these materials are modified then degradation may, depending on the degree of modification, be more difficult or even impossible. In the same manner synthesized macromolecules, whether from renewable or petrochemical sources, could be inert or completey biodegradable, depending on their chemical structure.     

Large deviations of realized volatility

This paper studies large and moderate deviation properties of a realized volatility statistic of high frequency financial data. We establish a large deviation principle for the realized volatility when the number of high frequency observations in a fixed time interval increases to infinity. Our large deviation result can be used to evaluate tail probabilities of the realized volatility. We also derive a moderate deviation rate function for a standardized realized volatility statistic. The moderate deviation result is useful for assessing the validity of normal approximations based on the central limit theorem. In particular, it clarifies that there exists a trade-off between the accuracy of the normal approximations and the path regularity of an underlying volatility process. Our large and moderate deviation results complement the existing asymptotic theory on high frequency data. In addition, the paper contributes to the literature of large deviation theory in that the theory is extended to a high frequency data environment.     

2-Halo-subsituted tetracenes: their generation and single crystal OFET characteristics

2-Chlorotetracene and 2-bromotetracene were generated in high purity from their monoketone precursors either by heating or upon irradiation of light. Crystals of two compounds were prepared by physical vapor transport method. Organic field effect transistors made with the single crystals of these two compounds were fabricated effectively. Their p-type transistor characteristics are described.     

Relaxation of shish‐kebab precursor in isotactic polystyrene after short‐term shear flow

We studied the formation and relaxation of precursors of shish‐kebab in isotactic polystyrene after applying pulse shear flow at temperatures above the nominal melting temperatures T_m (=223 °C). It was found that the string‐like objects that were assigned to precursors in a previous article appeared in micrometer scale up to ～285 °C, which was very close to the equilibrium melting temperature T (=289 °C), and the length and the diameter showed two‐step decays consisting of the fast and slow (almost nondecaying) components below ～270 °C, whereas the slow component disappeared above ～270 °C, suggesting that some mechanism stabilizing the string‐like objects disappeared at ～270 °C. It was also found that the two‐step decay was a nature of a single string‐like object, but not an average nature of many precursors, showing heterogeneous inner structure of the precursor. We discussed a possibility that the string‐like object had a fringed micelle type structure including large crystals with a melting temperature of ～270 °C. Within the proposed picture, the highest temperature for the precursor formation (～285 °C) was explained as a melting of the large crystals in oriented melt. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Hyperfine structure of ESR spectra as a probe for heisenberg exchange couplings in nitroxide triradicals serving as building blocks for molecule-based ferrimagnets

A study on electron spin resonance (ESR) spectroscopic determination of exchange interactions in organic oligoradicals is given. When the intramolecular exchange couplingJ between, unpaired electron spins in nitroxide-based oligoradicals falls within the order of 10 Oe (1 mK or 10^?3 cm^?1 forg=2), which is on the same order as the hyperfine couplingA of magnetic nuclei such as nitrogen atoms of nitroxide radicals, the magnitude ofJ can be determined from the hyperfine splitting pattern of ESR spectra in solutions. This range of the exchange couplingJ is not detectable in conventional magnetic susceptibility measurements. We demonstrate an application of hyperfine ESR spectroscopy as a probe for the exchange coupling to a series of organic oligoradicals, which the authors have recently developed as building blocks for molecule-based magnetic materials.     

Polymeric organosilicon systems 14. Synthesis and some properties of alternating polymers composed of a dithienylene group and a mono-, di- or tri-silanylene unit

Poly[5, 5′ - (dimethylsilylene) - 2, 2′ - dithienylene] (4a), poly[5, 5′ -(methylphenylsilylene)-2, 2′ -dithienylene] (4b), poly[5, 5′ -(1, 1, 2, 2-tetramethyldisilanylene)-2, 2′ -dithienylene] (4c), poly[5, 5′-(1, 2-dimethyl-1, 2-diphenyldisilanylene)-2, 2′ -dithienylene] (4d), poly[5, 5′-(1, 2, 2, 2-tetramethyldisilanylene)-2, 2′-dithienylene] (4e), and poly[5, 5′-(1, 1, 2, 2, 3, 3 - hexamethyltrisilanylene) - 2, 2′ -dithienylene] were synthesized by dehalogenative coupling of the respective bis(2-bromothienyl)- substituted mono, di- and tri-silanes with magnesium in the presence of a catalytic amount of a nickel(II) complex in 16–99% yields. The polymers thus obtained are light-yellow solids and soluble in common organic solvents. Molecular weights, M_w, of the polymers were measured and found to be 7800–35 000 by gel-permeation chromatography relative to polystyrene standards. The photochemical properties of the polymers (4a–4d) having silylene and disilanylene units were investigated. Only poly[5, 5′-(1, 2-dimethyl-1, 2-diphenyl-disilanylene)-2, 2′-dithienylene] (4d) was found to be photoactive, but the others were inactive. When the thin solid films prepared from the polymers 4a–4e by spin-coating were exposed to antimony(V) fluoride in vacuo, the films became conducting; their conductivities were determined to be 10^?2 – 10^?3 S cm^?1 by the four-probe method.     

Crystal structure of stable protein CutA1 from psychrotrophic bacterium Shewanella sp. SIB1

CutA1 is widely found in bacteria, plants and animals, including humans. The functions of CutA1, however, have not been well clarified. It is known that CutA1s from Pyrococcus horikoshii, Thermus thermophilus and Oryza sativa unfold at temperatures remarkably higher than the growth temperatures of the host organisms. In this work the crystal structure of CutA1 from the psychrotrophic bacterium Shewanella sp. SIB1 (SIB1-CutA1) in a trimeric form was determined at 2.7?? resolution. This is the first crystal structure of a psychrotrophic CutA1. The overall structure of SIB1-CutA1 is similar to those of CutA1 from Homo sapiens, Escherichia coli, Pyrococcus horikoshii, Thermus thermophilus, Termotoga maritima, Oryza sativa and Rattus norvergicus. A peculiarity is observed in the β2 strand. The β2 strand is divided into two short β strands, β2a and β2b, in SIB1-CutA1. A thermal denaturation experiment revealed that SIB1-CutA1 does not unfold completely at 363?K at pH 7.0, although Shewanella sp. SIB1 cannot grow at temperatures exceeding 303?K. These results indicate that the trimeric structural motif of CutA1 is the critical factor in its unusually high stability and suggest that CutA1 needs to maintain its high stability in order to function, even in psychrotrophs.