The vaporization rate of ice at temperatures near its melting point

The first study of free vaporization kinetics of ice at temperatures near its melting point is reported. The experimental approach employed is based on a unique combination of thermal desorption spectroscopy, microcalorimetry, and time-of-flight mass spectrometry, making it possible to overcome challenges associated with the introduction of volatile solids into a high vacuum environment. Measurements of the vaporization rate of polycrystalline ice demonstrate that the vaporization kinetics deviate dramatically from those predicted by a simple mobile precursor mechanism. The vaporization rate follows Arrhenius behavior from -40 to 0 degrees C with an effective activation energy of 50+/-4 kJ/mol, which is significantly higher than the value predicted by the simple mobile precursor mechanism. Extrapolation of earlier measurements conducted below -40 degrees C yields a value of approximately 0.02 at 0 degrees C for the vaporization coefficient alphav. In contrast, experimentally determined vaporization coefficient is found to be 0.7+/-0.3 and shows a weak dependence on temperature up to the bulk melting point. The role of possible surface phase transitions in the mechanisms of release and uptake of H2O and other chemical species by ice surfaces is discussed.     

Classification of the medicinal plants of the genus Atractylodes using high‐performance liquid chromatography with diode array and tandem mass spectrometry detection combined with multivariate statistical analysis

Analytical methods using high‐performance liquid chromatography with diode array and tandem mass spectrometry detection were developed for the discrimination of the rhizomes of four Atractylodes medicinal plants: A. japonica, A. macrocephala, A. chinensis, and A. lancea. A quantitative study was performed, selecting five bioactive components, including atractylenolide I, II, III, eudesma‐4(14),7(11)‐dien‐8‐one and atractylodin, on twenty‐six Atractylodes samples of various origins. Sample extraction was optimized to sonication with 80% methanol for 40 min at room temperature. High‐performance liquid chromatography with diode array detection was established using a C₁₈ column with a water/acetonitrile gradient system at a flow rate of 1.0 mL/min, and the detection wavelength was set at 236 nm. Liquid chromatography with tandem mass spectrometry was applied to certify the reliability of the quantitative results. The developed methods were validated by ensuring specificity, linearity, limit of quantification, accuracy, precision, recovery, robustness, and stability. Results showed that cangzhu contained higher amounts of atractylenolide I and atractylodin than baizhu, and especially atractylodin contents showed the greatest variation between baizhu and cangzhu. Multivariate statistical analysis, such as principal component analysis and hierarchical cluster analysis, were also employed for further classification of the Atractylodes plants. The established method was suitable for quality control of the Atractylodes plants.     

Acoustic hybrid junction in a rectangular waveguide

Acoustic scattering from a hybrid junction in a rectangular waveguide is studied. The Fourier transform and mode matching is used to represent the scattered wave and the simultaneous equations for the modal coefficients are formulated. A residue calculus is utilized to obtain a solution to the simultaneous equations in fast-converging series. Numerical computations are performed to show the behavior of transmission in terms of junction geometry and operating frequency. The utility of acoustic hybrid junction is discussed in terms of its decoupling characteristics.     

Hurst exponent and prediction based on weak-form efficient market hypothesis of stock markets

We empirically investigated the relationships between the degree of efficiency and the predictability in financial time-series data. The Hurst exponent was used as the measurement of the degree of efficiency, and the hit rate calculated from the nearest-neighbor prediction method was used for the prediction of the directions of future price changes. We used 60 market indexes of various countries. We empirically discovered that the relationship between the degree of efficiency (the Hurst exponent) and the predictability (the hit rate) is strongly positive. That is, a market index with a higher Hurst exponent tends to have a higher hit rate. These results suggested that the Hurst exponent is useful for predicting future price changes. Furthermore, we also discovered that the Hurst exponent and the hit rate are useful as standards that can distinguish emerging capital markets from mature capital markets.     

Solvent-modulated proton-coupled electron transfer in an iridium complex with an ESIPT ligand

Proton-coupled electron transfer (PCET), an essential process in nature with a well-known example of photosynthesis, has recently been employed in metal complexes to improve the energy conversion efficiency; however, a profound understanding of the mechanism of PCET in metal complexes is still lacking. In this study, we synthesized cyclometalated Ir complexes strategically designed to exploit the excited-state intramolecular proton transfer (ESIPT) of the ancillary ligand and studied their photoinduced PCET in both aprotic and protic solvent environments using femtosecond transient absorption spectroscopy and density functional theory (DFT) and time-dependent DFT calculations. The data reveal solvent-modulated PCET, where charge transfer follows proton transfer in an aprotic solvent and the temporal order of charge transfer and proton transfer is reversed in a protic solvent. In the former case, ESIPT from the enol form to the keto form, which precedes the charge transfer from Ir to the ESIPT ligand, improves the efficiency of metal-to-ligand charge transfer. This finding demonstrates the potential to control the PCET reaction in the desired direction and the efficiency of charge transfer by simply perturbing the external hydrogen-bonding network with the solvent.

The iridium complex with an ESIPT ligand shows solvent-modulated proton-coupled electron transfer, in which the temporal order of proton transfer and charge transfer is altered by the solvent environment.     

Isoflavone Changes in Immature and Mature Soybeans by Thermal Processing

The isoflavone changes occurring in mature soybeans during food processing have been well studied, but less information is available on the changes in immature soybeans during thermal processing. This study aimed to determine the effect of thermal processing by dry- or wet-heating on the changes in the isoflavone profiles of immature and mature soybeans. In the malonylglycoside forms of isoflavone, their deglycosylation was more severe after wet-heating than after dry-heating regardless of the soybean maturity. The malonyl forms of isoflavones in the immature seeds were drastically degraded after a short wet-heating process. In the acetylglycoside forms of isoflavone, dry-heating produced relatively low amounts of the acetyl types in the immature soybeans compared with those in the mature soybeans. These results were explained by the content of acetyldaidzin being relatively less changed after dry-heating immature soybeans but increasing four to five times in the mature soybeans. More of the other types of acetylglycoside were produced by dry-heating soybeans regardless of their maturity. Acetylgenistin in wet-heating was a key molecule because its content was unchanged in the immature soybeans during processing but increased in the mature soybeans. This determined the total acetylglycoside content after wet-heating. In contrast, most of the acetyl forms of isoflavone were produced after 90 to 120 min of dry-heating regardless of the seed maturity. It can be suggested that the pattern of isoflavone conversion was significantly affected by the innate water content of the seeds, with a lower water content in the mature soybeans leading to the greater production of acetyl isoflavones regardless of the processing method even if only applied for a relatively short time. The results suggested that the isoflavone conversion in the immature soybeans mainly follows the wet-heating process and can be promoted in the application of stronger processing.     

Clinical implications of proliferation activity in T1 or T2 male gastric cancer patients

Proliferation activity has already been established as a prognostic marker or as a marker for anticancer drug sensitivity. In gastric cancer, however, the prognostic significance of proliferation activity is still being debated. Several studies evaluating proliferation activity using Ki-67 have shown controversial results in terms of the relationship between proliferation activity and overall survival (OS) or drug sensitivity in gastric cancer patients. Because cytoskeleton-associated protein 2 (CKAP2) staining has recently been introduced as a marker of proliferation activity, we analyzed 437 gastric cancer tissues through CKAP2 immunohistochemistry, and we evaluated the chromatin CKAP2-positive cell count (CPCC) for proliferation activity. Although the CPCC did not show any significant correlation with OS in the male, female or total number of cases, it did show a significant correlation in the T1 or T2 male patient subgroup, according to log-rank tests (P=0.001) and univariate analysis (P=0.045). Additionally, multivariate analysis with the Cox proportional hazard regression model showed a significant correlation between the CPCC and OS (P=0.039) for the co-variables of age, gender, T stage, N stage, histology, tumor location, tumor size and adjuvant chemotherapy. In male gastric cancer cell lines, faster-growing cancer cells showed higher sensitivity to cisplatin than slow-growing cells. Thus our study indicates that CPCC-measured proliferation activity demonstrates a significantly worse prognosis in T1 or T2 male gastric cancer patients. The CPCC will help to more precisely classify gastric cancer patients and to select excellent candidates for adjuvant chemotherapy, which in turn will facilitate further clinical chemotherapeutic trials.     

Differential Regulation of Human Serotonin Receptor Type 3A by Chanoclavine and Ergonovine

Irritable bowel syndrome (IBS) is a chronic disease that causes abdominal pain and an imbalance of defecation patterns due to gastrointestinal dysfunction. The cause of IBS remains unclear, but intestinal-brain axis problems and neurotransmitters have been suggested as factors. In this study, chanoclavine, which has a ring structure similar to 5-hydroxytryptamine (5-HT), showed an interaction with the 5-HT_3A receptor to regulate IBS. Although its derivatives are known to be involved in neurotransmitter receptors, the molecular physiological mechanism of the interaction between chanoclavine and the 5-HT_3A receptor is unknown. Electrophysiological experiments were conducted using a two-electrode voltage-clamp analysis to observe the inhibitory effects of chanoclavine on Xenopus oocytes in which the h5-HT_3A receptor was expressed. The co-application of chanoclavine and 5-HT resulted in concentration-dependent, reversible, voltage-independent, and competitive inhibition. The 5-HT_3A response induced by 5-HT was blocked by chanoclavine with half-maximal inhibitory response concentration (IC₅₀) values of 107.2 µM. Docking studies suggested that chanoclavine was positioned close F130 and N138 in the 5-HT_3A receptor-binding site. The double mutation of F130A and N138A significantly attenuated the interaction of chanoclavine compared to a single mutation or the wild type. These data suggest that F130 and N138 are important sites for ligand binding and activity. Chanoclavine and ergonovine have different effects. Asparagine, the 130th amino acid sequence of the 5-HT_3A receptor, and phenylalanine, the 138th, are important in the role of binding chanoclavine, but ergonovine has no interaction with any amino acid sequence of the 5-HT_3A receptor. The results of the electrophysiological studies and of in silico simulation showed that chanoclavine has the potential to inhibit the hypergastric stimulation of the gut by inhibiting the stimulation of signal transduction through 5-HT_3A receptor stimulation. These findings suggest chanoclavine as a potential antiemetic agent for excessive gut stimulation and offer insight into the mechanisms of 5-HT_3A receptor inhibition.