Chiral SiO2 and Ag@SiO2 Materials Templated by Complexes Consisting of Comblike Polyethyleneimine and Tartaric Acid.

A facile avenue to fabricate micrometer-sized chiral (L-, D-) and meso-like (dl-) SiO2 materials with unique structures by using crystalline complexes (cPEI/tart), composed of comblike polyethyleneimine (cPEI) and L-, D-, or dl-tartaric acid, respectively, as catalytic templates is reported. Interestingly, both chiral crystalline complexes appeared as regularly left- and right-twisted bundle structures about 10 µm in length and about 5 µm in diameter, whereas the dl-form occurred as circular structures with about 10 µm diameter. Subsequently, SiO2 @cPEI/tart hybrids with high silica content (>55.0 wt %) were prepared by stirring a mixture containing tetramethoxysilane (TMOS) and the aggregates of the crystalline complexes in water. The chiral SiO2 hybrids and calcined chiral SiO2 showed very strong CD signals and a nanofiber-based morphology on their surface, whereas dl-SiO2 showed no CD activity and a nanosheet-packed disklike shape. Furthermore, metallic silver nanoparticles (Ag NPs) were encapsulated in each silica hybrid to obtain chiral (D and L forms) and meso-like (dl form) Ag@SiO2 composites. Also, the reaction between L-cysteine (Lcys) and these Ag@SiO2 composites was preliminarily investigated. Only chiral L- and D-Ag@SiO2 composites promoted the reaction between Lcys and Ag NPs to produce a molecular [Ag-Lcys]n complex with remarkable exciton chirality, whereas the reaction hardly occurred in the case of meso-like (dl-) Ag@SiO2 composite.

Evaluating the effect of the incidence angle of ALOS-2 PALSAR-2 on detecting aquaculture facilities for sustainable use of coastal space and resources.

Background: Driven by the growing world population, aquaculture plays a key role in meeting the increasing demand for food. However, aquaculture facilities in Japan are widely installed in coastal waters where natural disasters, such as typhoons and tsunamis, might wash these facilities away, thereby interfering with maritime navigation safety. Therefore, it is imperative to efficiently monitor the state of aquaculture facilities daily, particularly after a disaster in real time. To this end, several new space-borne L-band synthetic aperture radars (SARs) continue to be launched now and in the future, whose utilizations are expected to increase nationally and internationally. An example is the Japan Aerospace Exploration Agency, currently operating a SAR that can be operated day and night, and even under cloudy conditions, called ALOS-2 PALSAR-2. Methods: Based on the above facts, this study evaluated the effect of the incidence angle of ALOS-2 PALSAR-2 HH single-polarization data, using 3 m spatial resolution, on aquaculture raft detection. As the study site, we selected Ago Bay, located on the Pacific coast of Mie Prefecture in central Japan since the Nankai Trough Megathrust Earthquake and tsunamis have been predicted to occur in the future around this area. Then, we analyzed the sigma zero (backscattering coefficient) of aquaculture rafts and their surrounding sea surfaces, including the relationships between satellite orbits and aquaculture raft directions. Results: Investigations revealed that the optimum incidence angle for detecting aquaculture rafts in this study was 33.8°-45.1°. Differences in the sigma zero values existed between the ascending and descending orbits. However, the incidence angles differed on the orbits. Then, differences in the median sigma zero values across a range of incidence angles were evaluated under the descending orbit. In addition, when the directions of the aquaculture rafts were closely perpendicular to the satellite orbit, aquaculture rafts tended to show the highest values of sigma zero due to Bragg resonance scattering. Hence, this knowledge may allow for the rapid detection of aquaculture rafts during an emergency without going on-site.

Monitoring oyster culture rafts and seagrass meadows in Nagatsura-ura Lagoon, Sanriku Coast, Japan before and after the 2011 tsunami by remote sensing: their recoveries implying the sustainable development of coastal waters.

BACKGROUND: Coastal ecosystems are blue infrastructures that support coastal resources and also aquaculture. Seagrass meadows, one of coastal ecosystems, provide substrates for epiphytic diatoms, which are food resources for cultured filter feeder organisms. Highly intensive coastal aquaculture degrades coastal environments to decrease seagrass meadows. Therefore, efficient aquaculture management and conservation of seagrass meadows are necessary for the sustainable development of coastal waters. In ria-type bays, non-feeding aquaculture of filter feeders such as oysters, scallops, and ascidians are actively practiced along the Sanriku Coast, Japan. Before the 2011 Great East Japan Earthquake, the over-deployment of oyster culture facilities polluted the bottom environment and formed an hypoxic bottom water layer due to the organic excrements from cultured oysters. The tsunami in 2011 devastated the aquaculture facilities and seagrass meadows along the Sanriku Coast. We mapped the oyster culture rafts and seagrass meadows in Nagatsura-ura Lagoon, Sanriku Coast before and after the tsunami and monitored those and environments after the tsunami by field surveys. METHODS: We conducted field surveys and monitored the environmental parameters in Nagatsura-ura Lagoon every month since 2014. We used high-resolution satellite remote sensing images to map oyster culture rafts and seagrass meadows at irregular time intervals from 2006 to 2019 in order to assess their distribution. In 2019, we also used an unmanned aerial vehicle to analyze the spatial variability of the position and the number of ropes suspending oyster clumps beneath the rafts. RESULTS: In 2013, the number and distribution of the oyster culture rafts had been completely restored to the pre-tsunami conditions. The mean area of culture raft increased after the tsunami, and ropes suspending oyster clumps attached to a raft in wider space. Experienced local fishermen also developed a method to attach less ropes to a raft, which was applied to half of the oyster culture rafts to improve oyster growth. The area of seagrass meadows has been expanding since 2013. Although the lagoon had experienced frequent oyster mass mortality events in summer before the tsunami, these events have not occurred since 2011. The 2011 earthquake and tsunami deepened the sill depth and widened the entrance to enhance water exchange and improve water quality in the lagoon. These changes brought the expansion of seagrass meadows and reduction of mass mortality events to allow sustainable oyster culture in the lagoon. Mapping and monitoring of seagrass meadows and aquaculture facilities via satellite remote sensing can provide clear visualization of their temporal changes. This can in turn facilitate effective aquaculture management and conservation of coastal ecosystems, which are crucial for the sustainable development of coastal waters.

Cortisol promotes stress tolerance via DAF-16 in Caenorhabditis elegans.

In this study, we studied the effects of cortisol and cortisone on the age-related decrease in locomotion in the nematode Caenorhabditis elegans and on the tolerance to heat stress at 35 °C and to oxidative stress induced by the exposure to 0.1% H2O2. Changes in mRNA expression levels of C. elegans genes related to stress tolerance were also analyzed. Cortisol treatment restored nematode movement following heat stress and increased viability under oxidative stress, but also shortened worm lifespan. Cortisone, a cortisol precursor, also restored movement after heat stress. Additionally, cortisol treatment increased mRNA expression of the hsp-12.6 and sod-3 genes. Furthermore, cortisol treatment failed to restore movement of daf-16-deficient mutants after heat stress, whereas cortisone failed to restore the movement of dhs-30-deficient mutants after heat stress. In conclusion, the results suggested that cortisol promoted stress tolerance via DAF-16 but shortened the lifespan, whereas cortisone promoted stress tolerance via DHS-30.

Assessment of coastal anthropo-ecological system dynamics in response to a tsunami catastrophe of an unprecedented magnitude encountered in Japan.

On 11 March 2011, a catastrophic earthquake and subsequent tsunami hit the Pacific coast of northern Japan, devastating many of the towns, villages and coastal ecosystems located along the shoreline. To assess the impacts of the disaster, we investigated temporal dynamics of fish and epibenthic megafaunal community structure in relation to changes in a range of physical, biological and anthropogenic variables between 2007 and 2018 in Onagawa Bay. Commercially important fish such as greenlings, Japanese anchovy, flatfishes, rockfishes were consistently abundant in both larval and adult fish assemblages. While abundance, species richness, and Shannon index H' for adult fish and epibenthic megafaunal assemblages increased significantly soon after the disaster to peak values towards the end of the study period, the same metrics did not change accordingly for larval fish assemblages. Temporal dynamics of larval fish community clearly demonstrated significant seasonal variation along with changes in large-scale environmental conditions such as temperature and nutrients. However, anthropogenic components such as decline in human population, reduction in fishing pressure and the recovery of aquaculture operations significantly explained the observed post-disaster change in adult fish and epibenthic megafaunal communities. The pelagic and benthic components of Onagawa Bay appeared to have responded to the 2011 disaster very differently, and this study suggests the post-disaster recovery and dynamics of the coastal ecosystems may be regulated by how human societies respond to the impacts of a tsunami catastrophe through their influences on benthic habitat of ecosystems.

Escape dynamics of many hard disks.

Many-particle effects in escapes of hard disks from a square box via a hole are discussed in a viewpoint of dynamical systems. Starting from N disks in the box at the initial time, we calculate the probability P_{n}(t) for at least n disks to remain inside the box at time t for n=1,2,...,N. At early times, the probabilities P_{n}(t),n=2,3,...,N-1, are described by superpositions of exponential decay functions. On the other hand, after a long time the probability P_{n}(t) shows a power-law decay ∼t^{-2n} for n≠1, in contrast to the fact that it decays with a different power law ∼t^{-n} for cases without any disk-disk collision. Chaotic or nonchaotic properties of the escape systems are discussed by the dynamics of a finite-time largest Lyapunov exponent, whose decay properties are related with those of the probability P_{n}(t).

A comparative study of the rotational dynamics of PF6(-) anions in the crystals and liquid states of 1-butyl-3-methylimidazolium hexafluorophosphate: results from 31P NMR spectroscopy.

The rotational dynamics of the hexafluorophosphate anion (PF(6)(-)) in the crystalline and liquid states of the archetypal room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim]PF(6)) are investigated using (31)P NMR spectroscopy line shape analyses and spin-lattice relaxation time measurements. The PF(6)(-) anion performs isotropic rotation in all three polymorphic crystals phases α, ß, and γ as well as in the liquid state with a characteristic time scale that ranges from a few ps to a few hundred ps over a temperature range of 180-280 K. The rotational correlation time τ(c) for PF(6)(-) rotation follows the sequence γ-phase < α-phase ≈ liquid < ß-phase. On the other hand, in the liquid state, all local motions in the cation as well as its global rotational reorientation are characterized by time scales that are slower compared to that for the PF(6)(-) anion rotation. The time scale τ(c) and the activation energy of PF(6)(-) rotation in this RTIL are found to be comparable with those observed in ordinary alkali and ammonium salts despite the large counterion size and low melting point of the former. The high sphericity of the PF(6)(-) ion is hypothesized to play an important role in the decoupling of its rotational dynamics that appear to be practically independent of the averaged cation-anion interaction.

NMR study of cation dynamics in three crystalline states of 1-butyl-3-methylimidazolium hexafluorophosphate exhibiting crystal polymorphism.

We investigate the cation rotational dynamics of a room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim]PF(6)) in its three crystalline states by (1)H NMR spectroscopy. Spin-lattice and spin-spin relaxation time (T(1) and T(2), respectively) measurements as a function of temperature confirm the presence of three polymorphic crystals of [C(4)mim]PF(6): crystals α, ß, and γ, which we previously discovered using Raman spectroscopy and calorimetry. Second moment calculations of (1)H NMR spectra reveal that certain segmental motions of the butyl group in addition to the rapid rotation of the two methyl groups in the cation occur in all the crystals. The trend in the mobility of the segmental motions is γ < ß ≤ α, which is consistent with the strength of cation-anion interactions (or crystal packing density) estimated from high-frequency Raman scattering experiments. T(1) measurements demonstrate two types of rotational motions on the nanosecond time scale in all three crystals: fast and slow motions. The three crystals have similar activation energies of 12.5-15.1 kJ mol(-1) for the fast motion, which is assigned to the rotation of the methyl group at the terminal of the butyl group. These observed activation energies were consistent with that estimated by quantum chemical calculations in the gas phase (11.9 kJ mol(-1)). In contrast, the slow motions of crystals α and γ are attributed to different segmental motions of the butyl group and that of crystal ß to either a little segmental motion or a certain PF(6)(-) rotational motion. These nanosecond rotational motions obtained from the T(1) measurements do not appear to be affected by crystal packing density because local interactions in the crystalline state rather than packing density govern such nanosecond motions. With respect to the segmental motions, the mobility is likely to change significantly with the conformation of the butyl group. On the basis of these findings, crystal γ, which is the only crystalline phase previously determined using single-crystal X-ray diffraction, is considered to be the most stable phase because of the slowest segmental motions and the strongest cation-anion interactions.

Fecoflowmetric profiles in postoperative patients with Hirschsprung's disease.

PURPOSE: The objective of this study is to evaluate the anorectal function from the viewpoint of fecoflowmetry in postoperative patients with Hirschsprung's disease (HD). METHODS: This study evaluated 23 long-term follow-up patients who had undergone a radical operation for HD. Their mean age was 11 years. The types of HD included rectosigmoid colon type, 18 cases, and entire colon type, 5 cases. An anorectal manometric study was performed before fecoflowmetry. After normal saline solution was administrated as an imitation stool into the rectal cavity under pressure monitoring, the patients defecated on a fecoflowmeter. After discussing the maximum defecation flow (Flow-max), fecoflow pattern (FFP), tolerance rate (TR), anal canal pressure (AP), and Kelly's clinical scores (Kelly-Scores), the significant parameters were identified to elucidate the anorectal activity. RESULTS: (1) A close relationship was observed between the FFP and Kelly-Scores (P = .0027). (2) Flow-max, TR, and AP in patients with good Kelly-Scores were significantly higher than those in patients with fair Kelly-Scores (P < .05). (3) The Flow-max accurately reflected the TR, Kelly-Scores, and AP. Flow-max >45 mL per second, TR >70%, or AP >30 mm Hg was statistically regarded as a borderline level of fecal continence (P < .002). CONCLUSIONS: The Flow-max and FFP are considered to be useful parameters for postoperative patients with HD.

Embryonic development of the myenteric nerve plexus in the rat small intestine as revealed by light and scanning electron microscopy.

This study was performed to clarify developmental changes in the structure of the myenteric nerve plexus in the rat small intestine. The small intestines of fetal and neonatal rats were examined by light microscopic immunohistochemistry for protein gene product 9.5 (PGP-9.5) and alpha-smooth muscle actin (alpha-SMA). Direct observation of the three-dimensional structure of the neuronal and muscular elements was accomplished by scanning electron microscopy of tissues after KOH treatment. At the embryonic day 14 (E14), PGP-9.5 immunopositive (neuronal) cells first appeared in the mesenchymal tissue outside an alpha-SMA positive (muscle) cell layer. These cells increased in number to form a thin and continuous sheet, which was sandwiched between the inner and outer muscular layers at E17. This neuronal layer consisted of immature ganglion cells associated with supportive (enteroglial) cells, and was gradually segregated into groups by incomplete separation through slit-like interruptions at E18. With the widening of these slits at E19, the neuronal sheet was observed as a ladder composed of transversely elongated ganglia and their connecting nerve strands, resulting in the typical structure of the myenteric nerve plexus. Fibroblastic cells of a peculiar shape appeared on the outer surface of the myenteric plexus at E19. These cells (presumably interstitial cells) interconnected their long branching projections to form a cellular network on the myenteric plexus until birth.

Whole-blood manganese levels and brain manganese accumulation in children receiving long-term home parenteral nutrition.

Recent reports attribute neurological and cerebral disorders to the accumulation of manganese (Mn) in the brain in patients receiving home parenteral nutrition (HPN). It is desirable to control the amount of Mn delivered to these patients, but a suitable method for monitoring an individual's Mn status and assessing Mn accumulation remains debatable. The aim of this study was to evaluate whether whole-blood manganese levels (WB-Mn) correlate with the accumulation of Mn in the brains of children who receive long-term HPN, using magnetic resonance imaging (MRI) of the brain. Six patients who had received HPN (duration of HPN, 18-137 months) were included in this study. The daily parenteral doses of Mn were calculated while on HPN. WB-Mn was measured and T1-weighted MRI of the brain was obtained for each patient with a 1.5-T MR imager. Twelve months after the withdrawal of Mn from HPN, measurements of WB-Mn and brain MRI were repeated in all patients except for one who was lost after initial examination. The same examinations were performed on an additional patient who had been successfully weaned off a 179 month course of HPN 20 months prior to the initial examination. The parenteral dose of Mn while receiving HPN ranged from 15.7 to 91.5 micro g/kg/day. Initially, MRI showed hyperintensity in the globus pallidus in all patients and in the anterior pituitary in one patient. WB-Mn was elevated in four patients, but was in the normal range in the remaining three. Following subsequent measurements 12 months later, WB-Mn was normal in all patients and MRI hyperintensity remained in the globus pallidus in one patient. One patient was lost after the initial examinations. WB-Mn does not necessarily correlate with the accumulation of Mn in the brain. Periodic MRI should be performed in patients receiving long-term NPN to monitor for excessive Mn accumulation in the brain.