Chiral Reaction Field with Thermally Invertible Helical Sense that Controls the Helicities of Conjugated Polymers

A chiral reaction field with thermally invertible helical sense enables control of the helicity of the reaction product, which is a central challenge in asymmetric synthesis that has yet to be overcome. A novel chiral compound comprising two types of chiral moieties with opposite helicities and temperature dependences is synthesized; this compound is added as a chiral dopant to a mixture of nematic liquid crystals to prepare a chiral nematic liquid crystal (N*-LC). The N*-LC containing the chiral dopant exhibits thermally invertible helicity to yield left- and right-handed helical senses at low and high temperatures, respectively. Interfacial polymerization of acetylene is achieved in the N*-LC by modulating the temperature. Helical polyacetylenes (H-PAs) that are synthesized at low (−12 °C) and high (28 °C) temperature show right- and left-handedness, respectively, in terms of the fibrils, fibril bundles, and spiral morphology. In addition, the helical sense of H-PA is opposite that of the N*-LC because of the peculiar polymerization mechanism for acetylene in the N*-LC. The current N*-LC is the first chiral reaction field that has not only the thermally invertible helical sense but also the chemical functions and stability needed to serve as the medium for polymer reactions.     

Dependence of process characteristics on atomic-step density in catalyst-referred etching of 4H-SiC(0001) surface

Catalyst-referred etching (CARE) is a novel abrasive-free planarization method. CARE-processed 4H-SiC(0001) surfaces are extremely flat and undamaged over the whole wafer. They consist of single-bilayer-height atomic steps and atomically flat terraces. This suggests that the etching properties depend principally on the atomic-step density of the substrate surface. We used on-axis and 8 degrees off-axis substrates to investigate the processing characteristics that affect the atomic-step density of these substrates. We found a strong correlation between the removal rate and the atomic-step density of the two substrates. For the on-axis substrate, the removal rate increased with increasing surface roughness, which increases with an increasing atomic-step density. The removal rate ratio is approximately the same as the atomic-step density ratio of the two substrates.     

Efficient wet etching of GaN (0001) substrate with subsurface damage layer

Photoenhanced chemical (PEC) etching is applicable for processing an n-GaN (0001) surface rapidly. In this process, the surface oxidation is enhanced by photo-generated holes and the resulting oxide can dissolve into solutions. In current work, we conduct bias-assisted PEC etching in a KOH solution with a positively biased wafer, to remove the crystallographically highly damaged layer. The employed substrate was mechanically polished with diamond slurry of sub-micrometer particle size. Without the positive bias, the rate of PEC etching was quite low because the photogenerated holes were quickly depleted by the recombination process at the crystallographic defects and they could not contribute to the oxidation. On the other hand, in the case where the bias was applied, the photogenerated holes and electrons are separated forcibly in the band-bended surface, which effectively contributed to surface oxidation. As a result, a high removal rate was realized even on the damaged surface.     

Natural tubule clay template synthesis of silver nanorods for antibacterial composite coating

Halloysite is naturally available clay mineral with hollow cylindrical geometry and it is available in thousands of tons. Silver nanorods were synthesized inside the lumen of the halloysite by thermal decomposition of the silver acetate, which was loaded into halloysite from an aqueous solution by vacuum cycling. Images of individual ca. 15 nm diameter silver nanorods and nanoparticles were observed with TEM. The presence of silver inside the tubes was also verified with STEM-EDX elemental mapping. Nanorods had crystalline nature with [111] axis oriented ~68° from the halloysite tubule main axis. The composite of silver nanorods encased in clay tubes with the polymer paint was prepared, and the coating antimicrobial activity combined with tensile strength increase was demonstrated. Coating containing up 5% silver loaded halloysite did not change color after light exposure contrary to the sample prepared with loading with unshelled silver nanoparticles. Halloysite tube templates have a potential for scalable manufacturing of ceramic encapsulated metal nanorods for composite materials.     

Structural Analysis of Crystalline R(+)-α-Lipoic Acid-α-cyclodextrin Complex Based on Microscopic and Spectroscopic Studies

R(+)-α-lipoic acid (RALA) is a naturally-occurring substance, and its protein-bound form plays significant role in the energy metabolism in the mitochondria. RALA is vulnerable to a variety of physical stimuli, including heat and UV light, which prompted us to study the stability of its complexes with cyclodextrins (CDs). In this study, we have prepared and purified a crystalline RALA-αCD complex and evaluated its properties in the solid state. The results of ¹H NMR and PXRD analyses indicated that the crystalline RALA-αCD complex is a channel type complex with a molar ratio of 2:3 (RALA:α-CD). Attenuated total reflection/Fourier transform infrared analysis of the complex showed the shift of the C=O stretching vibration of RALA due to the formation of the RALA-αCD complex. Raman spectroscopic analysis revealed the significant weakness of the S–S and C–S stretching vibrations of RALA in the RALA-αCD complex implying that the dithiolane ring of RALA is almost enclosed in glucose ring of α-CD. Extent of this effect was dependent on the direction of the excitation laser to the hexagonal morphology of the crystal. Solid-state NMR analysis allowed for the chemical shift of the C=O peak to be precisely determined. These results suggested that RALA was positioned in the α-CD cavity with its 1,2-dithiolane ring orientated perpendicular to the plane of the α-CD ring.     

Non-Genetic Diversity in Chemosensing and Chemotactic Behavior

Non-genetic phenotypic diversity plays a significant role in the chemotactic behavior of bacteria, influencing how populations sense and respond to chemical stimuli. First, we review the molecular mechanisms that generate phenotypic diversity in bacterial chemotaxis. Next, we discuss the functional consequences of phenotypic diversity for the chemosensing and chemotactic performance of single cells and populations. Finally, we discuss mechanisms that modulate the amount of phenotypic diversity in chemosensory parameters in response to changes in the environment.     

Production of recombinant human lysosomal acid lipase in Schizosaccharomyces pombe: development of a fed-batch fermentation and purification process

A fed-batch fermentation process has been developed to enable the production of large quantities of recombinant human lysosomal acid lipase (hLAL; EC 3.1.1.13), in Schizosaccharomyces pombe, for preclinical studies as a potential enzyme therapy drug. Recombinant S. pombe, clone ASP397-21, expressed enzymatically active hLAL in the secreted form. A feedback fed-batch system was used to determine the optimal feed rate of a 50% glucose solution used as the carbon source. The feed rate of the glucose solution was calculated by a computer-aided system according to the equation; F=q(sf)(VX)/S(in) (q(sf), specific substrate feed rate [gram substrate/gram dry cell weight/h]; V, volume of culture broth [l]; X, cell density [gram dry cell weight/l]; S(in), concentration of growth limiting substrate in feed solution [gram substrate/gram feed solution]). At the time of the initial consumption of glucose in the batch-phase culture, the nutrient supply was automatically initiated by means of monitoring the respiratory quotient change. The obtained profile of the feed rate was applied to the feed forward control fermentation. Finally, the cells were grown up to >50 g dry cell weight/l, and the hLAL expression level was approximately 16,000 U/l. Expressed hLAL protein was purified in a two-step process by hydrophobic interaction and anion exchange chromatographies. Purified recombinant hLAL exhibited a 90-150 kDa broad band upon SDS-PAGE with specific activity of about 300 U/mg. After endoglycosidase H treatment, the band converged to 45 kDa, equal to the calculated molecular weight, suggesting that hLAL produced in S. pombe was hyper-glycosylated. N-terminal analysis of de-glycosylated hLAL revealed that the signal sequence of hLAL was correctly processed in S. pombe.     

Formation of protein adducts of 2‐amino‐1‐methyl‐6‐phenylimidazo[4,5‐b]pyridine in cooked foods

Heterocyclic amines (HCAs) are mutagenic and carcinogenic compounds found in cooked meat and fish. Although HCAs are known to form adducts with protein after metabolic activation, adduct formation during cooking has not been elucidated. In this study, we showed that 2‐amino‐1‐methyl‐6‐phenylimidazo[4,5‐b]pyridine (PhIP) is released from high molecular weight compounds by acid or enzymatic hydrolysis of cooked foods. Formation of free and protein adduct forms of PhIP was dependent on cooking temperature and time, and PhIP–protein adducts were estimated to form after formation of free PhIP. We also demonstrated that PhIP–protein adduct is formed by heating of PhIP and albumin as a model protein. A new adduct peak including [M+H]⁺ (m/z=225) of PhIP as a fragment ion was detected in the high molecular weight fraction of heat‐treated protein by LC–MS analysis. From model experiments by heating of PhIP and amino acids, the adduct was estimated to be produced by condensation of the amino group of PhIP and the carboxyl group of protein. PhIP–protein adducts were detected in several cooked meat and fish at ng/g food level as PhIP content. These results suggest that food‐borne protein adducts of HCAs may influence human HCA exposure and carcinogenic risk.     

Improvements in time resolution and signal-to-noise ratio in a compact pico-second pulse radiolysis system

A compact pico-second pulse radiolysis system has been developing at Waseda University for studying primary processes in radiation chemistry. The system is composed of a photo-injector system and a pico-second all-solid-state laser system. An infrared (IR) and an ultraviolet (UV) laser pulses are obtained from mode-locked Nd:YLF laser system and used for generation of the white light continuum as a probe light and the irradiation to the Cu cathode of a photo-cathode RF-gun, respectively. To improve signal-to-noise (S/N) ratio and time resolution of this pulse radiolysis system, we optimized both probe light and pump electron beam. As a result, our pico-second pulse radiolysis system has been enough to study the primary processes of radiation chemistry. The experimental results and the improvements of our system are described in this paper.     

Inhibition of the Phospholipase Cε–c-Jun N-Terminal Kinase Axis Suppresses Glioma Stem Cell Properties

Glioma stem cells (GSCs), the cancer stem cells of glioblastoma multiforme (GBM), contribute to the malignancy of GBM due to their resistance to therapy and tumorigenic potential; therefore, the development of GSC-targeted therapies is urgently needed to improve the poor prognosis of GBM patients. The molecular mechanisms maintaining GSCs need to be elucidated in more detail for the development of GSC-targeted therapy. In comparison with patient-derived GSCs and their differentiated counterparts, we herein demonstrated for the first time that phospholipase C (PLC)ε was highly expressed in GSCs, in contrast to other PLC isoforms. A broad-spectrum PLC inhibitor suppressed the viability of GSCs, but not their stemness. Nevertheless, the knockdown of PLCε suppressed the survival of GSCs and induced cell death. The stem cell capacity of residual viable cells was also suppressed. Moreover, the survival of mice that were transplanted with PLCε knockdown-GSCs was longer than the control group. PLCε maintained the stemness of GSCs via the activation of JNK. The present study demonstrated for the first time that PLCε plays a critical role in maintaining the survival, stemness, and tumor initiation capacity of GSCs. Our study suggested that PLCε is a promising anti-GSC therapeutic target.