Strength of fibers from wholly aromatic polyesters

A theory of the strength (or the tenacity) of highly oriented Liquid Crystal Polymer (LCP) fibers was developed, and its results were compared with existing tensile strength data of fibers of a copolymer of 1,4-oxybenzoate and 6,2-oxynaphthoate. A basic premise of the theory is that the mechanical load transfer between polymer chains is through intermolecular interaction which acts in a manner similar to that of shear stress, and that the fiber strength is primarily governed by the intermolecular adhesion strength. The theory also incorporates the effects of MW, MW distribution, and the chain orientation distribution. Analysis of the experimental tenacity data demonstrates that the present theory can quantitatively describe the variation of the tenacity of LCP fibers with MW both in the as-spun and in the heat-treated states. The theory further predicts that the predominant factor governing the tenacity of LCP fibers is primarily due to MW increase due to solid-state polymerization. It is also demonstrated that the intermolecular adhesion between LCP chains is relatively weak and does not improve with heat treatment. The absence of factors that limit the MW increase (i.e, imbalanced end-groups and side reactions of end groups) is a prerequisite for fast heat treatment of a LCP fiber to a high tenacity.Symbols A _f the cross-sectional area of a single polymer chain - E _f the theoretical modulus of a polymer chain - G _m the shear modulus of fiber - h(l) the chain length distribution function - l the chain length - l the number average chain length - l _c the length of chain units that are bonded to adjacent polymer chains - n ² 4G _m/CE_f - N _c the number of polymer chains per unit area perpendicular to the fiber axis - P _b the probability that a chain does not have a chain end in the fracture zone - P _e the probability that a chain has, at least, a chain end in the fracture zone - q _e,q _b the probability of finding an ending and a bridging polymer chain, respectively, in the fracture zone - l the length of fracture zone - the elongation of a polymer chain - the chain orientation angle - _f the normal stress that acts on a polymer chain - _fu the fiber tenacity - _e the shear stress that acts on a polymer chain surface Dedicated to Prof. Dr. rer. nat. Wolfgang Hilger, Chairman of Hoechst A.G. in honor of his 60th birthday     

Excitation-energy migration in self-assembled cyclic zinc(II)-porphyrin arrays: a close mimicry of a natural light-harvesting system

The excitation-energy-hopping (EEH) times within two-dimensional cyclic zinc(II)-porphyrin arrays 5 and 6, which were prepared by intermolecular coordination and ring-closing metathesis reaction of olefins, were deduced by modeling the EEH process based on the anisotropy depolarization as well as the exciton-exciton annihilation dynamics. Assuming the number of energy-hopping sites N = 5 and 6, the two different experimental observables, that is, anisotropy depolarization and exciton-excition annihilation times, consistently give the EEH times of 8.0 +/- 0.5 and 5.3 +/- 0.6 ps through the 1,3-phenylene linkages of 5 and 6, respectively. Accordingly, the self-assembled cyclic porphyrin arrays have proven to be well-defined two-dimensional models for natural light-harvesting complexes.     

Pressure-driven sample injection with quantitative liquid dispensing for on-chip electrophoresis.

A novel pressure-driven sample injection method was developed as an alternative to electrokinetic injection, and electrophoretic separation was carried out on a microfabricated device employing this method. This method enables a defined volume of liquid dispensing, followed by instantaneous injection driven by pneumatic pressure, greatly simplifying the injection procedure. A particular microstructure, called a "metering chamber", has been designed for the quantitative dispensing of an ultra-low volume of sample liquid; a "hydrophobic passive valve" equipped with an air vent channel is employed for injecting a dispensed sample into the separation channel. The reproducibility of dispensing was 3.3% (n = 15), expressed by the variation of dispensed volumes. The electrophoretic separation of DNA fragments was performed using this injection method, varying the injection volumes from 0.45 to 4.0 nL, and the separation efficiencies were compared. This precise injection method, easily variable in injection volumes, is highly suitable for quantitative as well as qualitative electrophoretic analyses.     

Changes in Isoflavone Profile from Soybean Seeds during Cheonggukjang Fermentation Based on High-Resolution UPLC-DAD-QToF/MS: New Succinylated and Phosphorylated Conjugates

In this study, thirty-eight isoflavone derivatives were comprehensively identified and quantified from the raw, steamed and fermented seeds of four selected soybean cultivars based on UPLC-DAD-QToF/MS results with reference to the previously reported LC-MS library and flavonoid database, and summarized by acylated group including glucosides (Glu), malonyl-glucosides (Mal-Glu), acetyl-glucosides (Ac-Glu), succinyl-glucosides (Suc-Glu) and phosphorylated conjugates (Phos) in addition to aglycones. Among them, Suc-Glu and Phos derivatives were newly generated due to fermentation by B. subtilis AFY-2 (cheonggukjang). In particular, Phos were characterized for the first time in fermented soy products using Bacillus species. From a proposed roadmap on isoflavone-based biotransformation, predominant Mal-Glu (77.5–84.2%, raw) decreased rapidly by decarboxylation and deesterification into Ac-Glu and Glu (3.5–8.1% and 50.0–72.2%) during steaming, respectively. As fermentation continued, the increased Glu were mainly succinylated and phosphorylated as well as gradually hydrolyzed into their corresponding aglycones. Thus, Suc-Glu and Phos (17.3–22.4% and 1.5–5.4%, 36 h) determined depending on cultivar type and incubation time, and can be considered as important biomarkers generated during cheonggukjang fermentation. Additionally, the changes of isoflavone profile can be used as a fundamental report in applied microbial science as well as bioavailability research from fermented soy foods.     

Dynamic mechanical properties of metallic glasses

Dynamic mechanical properties of two metallic glasses, Fe₄₀Ni₄₀P₁₄B₆ and Fe₃₂Ni₃₆Cr₁₄P₁₂B₆, have been studied at frequencies ranging from 0.1 to 3 kHz and at temperatures between ? 160 and 390°C. Each of the samples exhibits an internal friction maximum at about ?20°C with activation energies of 25 and 34 kcal/mol. A possible mechanism for the low-temperature internal friction peak is suggested.     

Identification of New Non-BBB Permeable Tryptophan Hydroxylase Inhibitors for Treating Obesity and Fatty Liver Disease

Serotonin (5-hydroxytryptophan) is a hormone that regulates emotions in the central nervous system. However, serotonin in the peripheral system is associated with obesity and fatty liver disease. Because serotonin cannot cross the blood-brain barrier (BBB), we focused on identifying new tryptophan hydroxylase type I (TPH1) inhibitors that act only in peripheral tissues for treating obesity and fatty liver disease without affecting the central nervous system. Structural optimization inspired by para-chlorophenylalanine (pCPA) resulted in the identification of a series of oxyphenylalanine and heterocyclic phenylalanine derivatives as TPH1 inhibitors. Among these compounds, compound 18i with an IC₅₀ value of 37 nM was the most active in vitro. Additionally, compound 18i showed good liver microsomal stability and did not significantly inhibit CYP and Herg. Furthermore, this TPH1 inhibitor was able to actively interact with the peripheral system without penetrating the BBB. Compound 18i and its prodrug reduced body weight gain in mammals and decreased in vivo fat accumulation.     

Observation of insulating–insulating monoclinic structural transition in macro‐sized VO2 single crystals [Phys. Status Solidi RRL 5, No. 3, R107–R109 (2011)]

In our article, we reported the observation of monoclinic M2 to M1 structural phase transition in VO₂ single crystal near the temperature of ～49 °C. However, the re‐examination of Laue patterns reveals that previously defined monoclinic M1 and M2 phases can be interpreted as monoclinic M2 and triclinic T phases instead. Careful experimental geometry calibration and further refinement of the lattice parameter ratios and angles show that monoclinic M2 and triclinic T phases fit better with the experimental data. On the other hand, our previous misidentification of the insulating phases does NOT affect the conclusions of our article. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Tomatidine-stimulated maturation of human embryonic stem cell-derived cardiomyocytes for modeling mitochondrial dysfunction

Human embryonic stem cell-derived cardiomyocytes (hESC-CMs) have been reported to exhibit immature embryonic or fetal cardiomyocyte-like phenotypes. To enhance the maturation of hESC-CMs, we identified a natural steroidal alkaloid, tomatidine, as a new substance that stimulates the maturation of hESC-CMs. Treatment of human embryonic stem cells with tomatidine during cardiomyocyte differentiation stimulated the expression of several cardiomyocyte-specific markers and increased the density of T-tubules. Furthermore, tomatidine treatment augmented the number and size of mitochondria and enhanced the formation of mitochondrial lamellar cristae. Tomatidine treatment stimulated mitochondrial functions, including mitochondrial membrane potential, oxidative phosphorylation, and ATP production, in hESC-CMs. Tomatidine-treated hESC-CMs were more sensitive to doxorubicin-induced cardiotoxicity than the control cells. In conclusion, the present study suggests that tomatidine promotes the differentiation of stem cells to adult cardiomyocytes by accelerating mitochondrial biogenesis and maturation and that tomatidine-treated mature hESC-CMs can be used for cardiotoxicity screening and cardiac disease modeling.Subject terms: Heart failure, Embryonic stem cells, Stem-cell differentiation