Single-crystalline oligomer-based conductors modeling the doped poly(3,4-ethylenedioxythiophene) family.

Conductive polymers with highly conjugated systems, such as the doped poly(3,4-ethylenedioxythiophene) (PEDOT) family, are commonly used in organic electronics. However, their structural inhomogeneity with various chain lengths makes it difficult to control their conductivities and structural details. On the other hand, low-molecular-weight materials have well-defined structures but relatively narrow conjugate areas with a limited range of Coulomb repulsion between carriers (Ueff), which hamper the flexible control of conductivities. To bridge this gap, we developed oligomer-based conductors, which are intermediate materials between polymers and low-molecular-weight materials. Using a library of single-crystal charge-transfer salts of oligo(3,4-ethylenedioxythiophene) (oligoEDOT) analogs that model the doped PEDOT family, we have investigated the structure-determining factors affecting their conductivities, such as counter anion variations, lengths of oligomer donor, and band fillings. Through the screening study, we developed oligoEDOT analogs with tunable room temperature conductivities by several orders of magnitude, including a metallic state above room temperature. In this study, we consistently evaluated the electronic structural insights by first-principles calculations and revealed that Ueff is the dominant factor that determines the relationship between the structures and conductivities. The unique features of oligoEDOT conductor systems with widely variable Ueff can differentiate these systems from strongly electron-correlated systems.

Halogen-Bonding-Promoted Photoinduced C-X Borylation of Aryl Halide Using Phenol Derivatives.

This study investigates the photoinduced C-X borylation reaction of aryl halides by forming a halogen-bonding (XB) complex using 2-naphthol as an XB acceptor. The method is chemoselective and broadly functional group tolerant and provides concise access to corresponding boronate esters. Mechanistic studies reveal that forming the XB complex between aryl halide and naphthol acts as an electron donor-acceptor complex to furnish aryl radicals through photoinduced electron transfer.

Screening of flavor compounds using Ucp1-luciferase reporter beige adipocytes identified 5-methylquinoxaline as a novel UCP1-inducing compound.

Uncoupling protein 1 (UCP1) in brown or beige adipocytes is a mitochondrial protein that is expected to enhance whole-body energy expenditure. For the high-throughput screening of UCP1 transcriptional activity regulator, we established a murine inguinal white adipose tissue-derived Ucp1-luciferase reporter preadipocyte line. Using this reporter preadipocyte line, 654 flavor compounds were screened, and a novel Ucp1 expression-inducing compound, 5-methylquinoxaline, was identified. Adipocytes treated with 5-methylquinoxaline showed increased Ucp1 mRNA expression levels and enhanced oxygen consumption. 5-Methylquinoxaline induced Ucp1 expression through peroxisome proliferator-activated receptor γ coactivator 1α (PGC1α), and 5-methylquinoxaline-induced PGC1α activation seemed to be partially regulated by its phosphorylation or deacetylation. Thus, our Ucp1-luciferase reporter preadipocyte line is a useful tool for screening of Ucp1 inductive compounds.

Enhancement of Ablative Rayleigh-Taylor Instability Growth by Thermal Conduction Suppression in a Magnetic Field.

Ablative Rayleigh-Taylor instability growth was investigated to elucidate the fundamental physics of thermal conduction suppression in a magnetic field. Experiments found that unstable modulation growth is faster in an external magnetic field. This result was reproduced by a magnetohydrodynamic simulation based on a Braginskii model of electron thermal transport. An external magnetic field reduces the electron thermal conduction across the magnetic field lines because the Larmor radius of the thermal electrons in the field is much shorter than the temperature scale length. Thermal conduction suppression leads to spatially nonuniform pressure and reduced thermal ablative stabilization, which in turn increases the growth of ablative Rayleigh-Taylor instability.

Photoinduced Atom Transfer Radical Addition Reaction of Olefins with α-Bromo Carbonyls.

The irradiation of halogen-bonded complexes with light leads to the homolysis of carbon-halogen bonds and the formation of the corresponding carbon radical species. However, the only methodology reported for these halogen-bonding complexes is using CBr4 as the halogen-bond donor and its applicability is of great interest. In this study, the atom transfer radical addition (ATRA) reaction of olefins using bromomalonates as halogen-bonding donors was developed. Using 4-phenylpyridine as the halogen-bonding acceptor, the desired reaction proceeded well under external irradiation of 380 nm light to furnish the corresponding ATRA reaction product. The ATRA reaction was effective in generating the corresponding products for a variety of olefins. Furthermore, the ATRA reaction was applicable to bulky ketones, substrates, and malonate esters. The intermediates of the reaction were identified and a plausible reaction mechanism was proposed.

Photoinduced Atom Transfer Radical Addition/Cyclization Reaction between Alkynes or Alkenes with Unsaturated α-Halogenated Carbonyls.

We have developed a photochemical ATRA/ATRC reaction that is mediated by halogen bonding interactions. This reaction is caused by the reaction of malonic acid ester derivatives containing bromine or iodine with unsaturated compounds such as alkenes and alkynes in the presence of diisopropylethylamine under visible light irradiation. As a result of various control experiments, it was found that the formation of complexes between amines and halogens by halogen-bonding interaction occurs in the reaction system, followed by the cleavage of the carbon-halogen bonds by visible light, resulting in the formation of carbon radicals. In this reaction, a variety of substrates can be used, and the products, cyclopentenes and cyclopentanes, were obtained by intermolecular addition and intramolecular cyclization.

Petapascal Pressure Driven by Fast Isochoric Heating with a Multipicosecond Intense Laser Pulse.

Fast isochoric laser heating is a scheme to heat matter with a relativistic intensity (>10^{18} W/cm^{2}) laser pulse for producing an ultrahigh-energy-density (UHED) state. We have demonstrated an efficient fast isochoric heating of a compressed dense plasma core with a multipicosecond kilojoule-class petawatt laser and an assistance of externally applied kilotesla magnetic fields for guiding fast electrons to the dense plasma. A UHED state of 2.2 PPa is achieved experimentally with 4.6 kJ of total laser energy that is one order of magnitude lower than the energy used in the conventional implosion scheme. A two-dimensional particle-in-cell simulation confirmed that diffusive heating from a laser-plasma interaction zone to the dense plasma plays an essential role to the efficient creation of the UHED state.

In Situ-Generated Halogen-Bonding Complex Enables Atom Transfer Radical Addition (ATRA) Reactions of Olefins.

Although organic-based photocatalysts provide an inexpensive, environmentally friendly alternative, many are incapable of absorption within the visible wavelength range; this ultimately influences their effectiveness. Photocatalytic reactions usually proceed via single electron transfer (SET) or energy transfer (ET) processes from the photoexcited molecules to the various substrates. In our study, the carbohalogenation of olefins was accomplished by combining CBr4 and 4-Ph-pyridine under irradiation. The atom transfer radical addition reaction of olefins was catalyzed by an in situ-formed photocatalyst via halogen bonding to afford a variety of products in moderate to good yields. Essential to the reaction is the formation of a CT complex with the haloalkene, which triggers charge separation processes and, ultimately, leads to the formation of the C-centered radical. While taking advantage of relatively inexpensive, readily available, and environmentally friendly reagents, the indirect activation of the substrate via the photoexcited catalyst paves the way for more efficient routes, especially for otherwise challenging chemical syntheses.

Application of Bio-Impedance Analysis to Estimate the Condition of Yellowtail (Seriola quinqueradiata) Muscle at Different Storage Temperatures.

Changes in impedance at 2 kHz, adenosine triphosphate (ATP) content, and muscle contraction were evaluated in yellowtail during 0 (ice), 5, 10, 15, and 20°C storage. Histological changes during ice storage were also measured. At any temperature, although impedance increased with both rigor mortis and ATP consumption during early storage, it began to decrease rapidly when ATP was almost depleted. Moreover, temporarily increasing impedance had a strong relationship with ATP content; decreasing impedance had a significant correlation with storage temperature after ATP depletion. Furthermore, impedance increased with narrowing of intercellular spaces when sarcolemma was intact and decreased with expansion of intercellular spaces when sarcolemma was leaky. Meanwhile, changes of sarcolemma and intercellular spaces were accompanied by ATP change. Thus, ATP is one significant physiological factor for impedance change, and temperature greatly influenced impedance after depletion of ATP. Results suggest that impedance analysis can be used as a convenient and nondestructive method to diagnose condition of tissue at different storage temperatures. Bioelectromagnetics. 2019;40:488-497. © 2019 Bioelectromagnetics Society.

Orbital hybridization of donor and acceptor to enhance the conductivity of mixed-stack complexes.

Mixed-stack complexes which comprise columns of alternating donors and acceptors are organic conductors with typically poor electrical conductivity because they are either in a neutral or highly ionic state. This indicates that conductive carriers are insufficient or are mainly localized. In this study, mixed-stack complexes that uniquely exist at the neutral-ionic boundary were synthesized by combining donors (bis(3,4-ethylenedichalcogenothiophene)) and acceptors (fluorinated tetracyanoquinodimethanes) with similar energy levels and orbital symmetry between the highest occupied molecular orbital of the donor and the lowest unoccupied molecular orbital of the acceptor. Surprisingly, the orbitals were highly hybridized in the single-crystal complexes, enhancing the room-temperature conductivity (10-4-0.1 S cm-1) of mixed-stack complexes. Specifically, the maximum conductivity was the highest reported for single-crystal mixed-stack complexes under ambient pressures. The unique electronic structures at the neutral-ionic boundary exhibited structural perturbations between their electron-itinerant and localized states, causing abrupt temperature-dependent changes in their electrical, optical, dielectric, and magnetic properties.

[Reliability of HOMA-IR for evaluation of insulin resistance during perioperative period].

BACKGROUND: Hyperglycemia due to increase in insulin resistance (IR) is often observed after surgery in spite of normal insulin secretion. To evaluate the degree of IR, the golden standard method is the normoglycemic hyperinsulinemic clamp technique (glucose clamp: GC). The GC using the artificial pancreas, STG-22 (Nikkiso, Tokyo, Japan), was established as a more reliable method, since it was evaluated during steady-state period under constant insulin infusion. Homeostasis model assessment insulin resistance (HOMA-IR), however, is frequently employed in daily practice because of its convenience. We, therefore, investigated the reliability of HOMA-IR in comparison with the glucose clamp using the STG-22. METHODS: Eight healthy patients undergoing maxillofacial surgery were employed in this study after obtaining written informed consent. Their insulin resistance was evaluated by HOMA-IR and the GC using the STG-22 before and after surgery. RESULTS: HOMA-IR increased from 0.81 +/- 0.48 to 1.17 +/- 0.50, although there were no significant differences between before and after surgery. On the other hand, M-value by GC significantly decreased after surgery from 8.82 +/- 2.49 mg x kg(-1) x min(-1) to 3.84 +/- 0.79 mg x kg(-1) x min(-1) (P = 0.0003). In addition, no significant correlation was found between the values of HOMA-IR and the M-value by GC. CONCLUSIONS: HOMA-IR may not be reliable to evaluate IR for perioperative period.

Fabrication and Characterization of Oleofoams Composed of Tribehenoyl-glycerol: Toward a Stable and Higher Air-content Colloidal System.

Oleofoams have garnered significant attention in many personal care applications because of their favorable physicochemical properties, including texture and detergency. To explore the potential use of mixtures of high-melting-point fat crystals (tribehenoyl-glycerol [BBB]) and edible oils as low-cost and stable aeration systems, we created oleofoams composed of olive oil and BBB. By whipping the BBB/olive oil oleogels after rapid cooling and subsequent heating, we successfully prepared oleofoams without emulsifier additives. Mixtures of the BBB/olive oil formed oleofoams at BBB concentrations of 4.0-20.0 wt.%. The resultant oleofoams maintained their overrun rates and did not coalesce, even with additional whipping after the overrun rate was maximized. More closely packed bubbles, concentrated bubble size distributions, and stronger interfacial elasticity were attributed to the increasing BBB concentrations, and the thermal results revealed that further heating was required to damage the foam structure. The characteristics of these new oleofoams are closely related to their BBB concentrations, and the observed effects are attributed to the network structure of the thickened crystal layer and enhanced gelling in the oil phase.

Formation and Physical Analysis of Oleogels Composed of Edible Oils and High-Melting Fat Crystals.

This paper reports the preparation of oleogels composed of edible oils (olive oil, squalene, and caprylic/capric triglyceride) and high-melting fat crystals (tribehenoyl-glycerol (BBB)) to explore the potential use of BBB/edible oil mixtures as low-cost and stable gelators. These mixtures exhibited gel-like behaviors upon rapid cooling and subsequent heating. The mixtures of BBB in the liquid oils formed oleogels at BBB concentrations > 4.0 wt%. The thermal behaviors, crystal structures, and crystal morphologies of mixtures of BBB produced from 6.0 wt% BBB crystals in 94.0 wt% liquid oils were examined following the treatment of these systems according to different temperature regimes. In addition, rheological analysis was conducted to evaluate the physical properties and storage stabilities of the prepared oleogels. It was found that rapid cooling to the crystallization temperature (Tc) from 70°C and subsequent heating to the final temperature (Tf) were necessary to reveal the gel-like behavior. In addition, the crystals treated with rapid cooling were smaller and more uniform in size than those treated with a simple cooling procedure. The differential scanning calorimetry melting peaks were broad or split, and exhibited the eutectic mixing behavior of multi-component triacylglycerols. The X-ray diffraction spectra showed that the melt-mediated α to ß transformation of the mixtures was a prerequisite for revealing the gel-like behavior. Moreover, the tempering procedure was found to influence the physical properties of the oleogels, wherein no visible changes were observed for any of the oleogels after rapid cooling and storage for 6 months at 25°C.

Laser astrophysics experiment on the amplification of magnetic fields by shock-induced interfacial instabilities.

Laser experiments are becoming established as tools for astronomical research that complement observations and theoretical modeling. Localized strong magnetic fields have been observed at a shock front of supernova explosions. Experimental confirmation and identification of the physical mechanism for this observation are of great importance in understanding the evolution of the interstellar medium. However, it has been challenging to treat the interaction between hydrodynamic instabilities and an ambient magnetic field in the laboratory. Here, we developed an experimental platform to examine magnetized Richtmyer-Meshkov instability (RMI). The measured growth velocity was consistent with the linear theory, and the magnetic-field amplification was correlated with RMI growth. Our experiment validated the turbulent amplification of magnetic fields associated with the shock-induced interfacial instability in astrophysical conditions. Experimental elucidation of fundamental processes in magnetized plasmas is generally essential in various situations such as fusion plasmas and planetary sciences.

Magnetized fast isochoric laser heating for efficient creation of ultra-high-energy-density states.

Fast isochoric heating of a pre-compressed plasma core with a high-intensity short-pulse laser is an attractive and alternative approach to create ultra-high-energy-density states like those found in inertial confinement fusion (ICF) ignition sparks. Laser-produced relativistic electron beam (REB) deposits a part of kinetic energy in the core, and then the heated region becomes the hot spark to trigger the ignition. However, due to the inherent large angular spread of the produced REB, only a small portion of the REB collides with the core. Here, we demonstrate a factor-of-two enhancement of laser-to-core energy coupling with the magnetized fast isochoric heating. The method employs a magnetic field of hundreds of Tesla that is applied to the transport region from the REB generation zone to the core which results in guiding the REB along the magnetic field lines to the core. This scheme may provide more efficient energy coupling compared to the conventional ICF scheme.

Magnetohydrodynamics of laser-produced high-energy-density plasma in a strong external magnetic field.

Recent progress in the generation in the laboratory of a strong (>100-T) magnetic field enables us to investigate experimentally unexplored magnetohydrodynamics phenomena of a high-energy-density plasma, which an external magnetic field of 200-300 T notably affects due to anisotropic thermal conduction, even when the magnetic field pressure is much lower than the plasma pressure. The external magnetic field reduces electron thermal conduction across the external magnetic field lines because the Larmor radius of the thermal electrons in the external magnetic field is much shorter than the mean free path of the thermal electrons. The velocity of a thin polystyrene foil driven by intense laser beams in the strong external magnetic field is faster than that in the absence of the external magnetic field. Growth of sinusoidal corrugation imposed initially on the laser-driven polystyrene surface is enhanced by the external magnetic field because the plasma pressure distribution becomes nonuniform due to the external magnetic-field structure modulated by the perturbed plasma flow ablated from the corrugated surface.

Intra-operative administration of low-dose IV glucose attenuates post-operative insulin resistance.

BACKGROUND & AIMS: Insulin sensitivity often decreases after surgery in spite of normal insulin secretion, and may worsen the outcome. This post-operative insulin resistance increases according to the magnitude of surgical invasion. However, supplementation of carbohydrates before surgery attenuates the post-operative insulin resistance. This study aimed to investigate the effect of intra-operative administration of low-dose glucose on the post-operative insulin resistance. METHODS: Patients undergoing maxillofacial surgery were randomly assigned to two groups throughout the surgical procedure: The glucose group receiving acetated Ringer solution with 1.5% glucose and the control group receiving acetated Ringer solution without glucose. Insulin resistance quantified by the mean glucose infusion rate (the glucose infusion rate) was evaluated by glucose clamp using the STG-22TM instrument on the previous day and on the next day of surgery. Blood glucose level was monitored continuously during surgery. In addition, serum insulin, ketone bodies and 3-methylhistidine were measured during perioperative period. RESULTS: Patients in the glucose group (n=11) received 0.15 ± 0.06 g/kg/h of glucose during surgery, while patients in the control group (n=11) received no glucose. In both groups, however, the mean blood glucose levels were maintained stable at less than 150 mg/dL during and after surgery. The serum ketone bodies significantly increased after surgery in the control group (p=0.0035), while it decreased significantly in the glucose group (p=0.043). The reduction rate in the glucose infusion rate was significantly lower in the glucose group, 43.3 ± 20.7%, than that in the control group, 57.7 ± 9.3% (p=0.041). CONCLUSIONS: Intra-operative small-dose of glucose administration may suppress ketogenesis and attenuate the post-operative insulin resistance without causing hyperglycemia.

Distinct composition of the oral indigenous microbiota in South Korean and Japanese adults.

A comparison of national surveys on oral health suggested that the population of South Korea has a better periodontal health status than that of Japan, despite their similar inherent backgrounds. Here, we investigated differences in oral bacterial assemblages between individuals from those two countries. To exclude potential effects of oral health condition on the microbiota, we selected 52 Korean and 88 Japanese orally healthy adults (aged 40-79 years) from the participants of two cohort studies, the Yangpyeong study in South Korea and the Hisayama study in Japan, and compared the salivary microbiomes. The microbiota of the Japanese individuals comprised a more diverse community, with greater proportions of 17 bacterial genera, including Veillonella, Prevotella, and Fusobacterium, compared to the microbiota of the Korean individuals. Conversely, Neisseria and Haemophilus species were present in much lower proportions in the microbiota of the Japanese individuals than the Korean individuals. Because higher proportions of Prevotella and Veillonella and lower proportions of Neisseria and Haemophilus in the salivary microbiome were implicated in periodontitis, the results of this study suggest that the greater proportion of dysbiotic oral microbiota in the Japanese individuals is associated with their higher susceptibility to periodontitis compared to the Korean individuals.

Compositional stability of a salivary bacterial population against supragingival microbiota shift following periodontal therapy.

Supragingival plaque is permanently in contact with saliva. However, the extent to which the microbiota contributes to the salivary bacterial population remains unclear. We compared the compositional shift in the salivary bacterial population with that in supragingival plaque following periodontal therapy. Samples were collected from 19 patients with periodontitis before and after periodontal therapy (mean sample collection interval, 25.8 ± 2.6 months), and their bacterial composition was investigated using barcoded pyrosequencing analysis of the 16S rRNA gene. Phylogenetic community analysis using the UniFrac distance metric revealed that the overall bacterial community composition of saliva is distinct from that of supragingival plaque, both pre- and post-therapy. Temporal variation following therapy in the salivary bacterial population was significantly smaller than in the plaque microbiota, and the post-therapy saliva sample was significantly more similar to that pre-therapy from the same individual than to those from other subjects. Following periodontal therapy, microbial richness and biodiversity were significantly decreased in the plaque microbiota, but not in the salivary bacterial population. The operational taxonomic units whose relative abundances changed significantly after therapy were not common to the two microbiotae. These results reveal the compositional stability of salivary bacterial populations against shifts in the supragingival microbiota, suggesting that the effect of the supragingival plaque microbiota on salivary bacterial population composition is limited.