Calculation of the critical point for mixtures using mixture models based on Helmholtz energy equations of state

This paper mainly focuses on refrigerant mixtures with relatively simple critical behavior, and presents a practical and useful method for the critical point calculation for the mixtures using mixture models based on Helmholtz energy equations of state. The expression for critical point criterion suitable for this objective is derived first. Numerical manipulations to obtain a physically correct solution are described in detail. For four binary refrigerant mixtures of difluoromethane (R-32) + pentafluoroethane (R-125), R-125 + 1,1,1,2-tetrafluoroethane (R-134a), R-125 + 1,1,1-trifluoroethane (R-143a), and R-32 + propane (R-290), the critical temperatures and critical molar volumes are calculated applying the presented method. The calculation results are compared with experimental values, and the capabilities of the mixture models for the mixtures in the critical region are discussed.     

Enantioselective total synthesis of sacrolide A

An enantioselective total synthesis of sacrolide A, an antimicrobial and cytotoxic fourteen-membered macrolactonic oxylipin isolated from an edible freshwater cyanobacterium, has been accomplished from a known carboxylic acid in 20% overall yield by a concise ten-step sequence. The key transformations include chiral oxazolidinone-based diastereoselective installation of two hydroxy-bearing stereocenters, the Horner–Wadsworth–Emmons olefination to construct the full carbon skeleton, and the Shiina macrolactonization to establish the fourteen-membered macrolide structure.     

Medicinal Flowers. XXXI. Acylated oleanane-type triterpene saponins, Sasanquasaponins I-V, with antiallergic activity from the flower buds of Camellia sasanqua

The methanolic extract and its 1-butanol-soluble fraction from the flower buds of Camellia sasanqua THUNB. were found to show inhibitory activities on the release of β-hexosaminidase from rat basophile leukemia (RBL-2H3) cells. From the 1-butanol-soluble fraction, five new acylated oleanane-type triterpene saponins, sasanquasaponins I-V, were isolated together with a known saponin and their chemical structures were elucidated on the basis of chemical and physicochemical evidence. The principal saponin constituents, sasanquasaponins I-III, with an acyl group at the 22-position of the aglycon part showed the inhibitory effects on the release of β-hexosaminidase and some structure-activity relationships were reported.     

Precise and global identification of phospholipid molecular species by an Orbitrap mass spectrometer and automated search engine Lipid Search

In the present research, we have established a new lipidomics approach for the comprehensive and precise identification of molecular species in a crude lipid mixture using a LTQ Orbitrap mass spectrometer (MS) and reverse-phase liquid chromatography (RPLC) combination with our newly developed lipid search engine “Lipid Search”. LTQ Orbitrap provides high mass accuracy MS spectra by Fourier-transform (FT) mass spectrometer mode and can perform rapid MSⁿ by ion trap (IT) mass spectrometer mode. In this study, the negative ion mode was selected to detect fragment ions from phospholipids, such as fatty acid anions, by MS2 or MS3. We selected the specific detection approach by neutral loss survey-dependent MS3, for the identification of molecular species of phosphatidylcholine, sphingomyelin and phosphatidylserine. Identification of molecular species was performed by using both the high mass accuracy of the mass spectrometric data obtained from FT mode and structural data obtained from fragments in IT mode. Some alkylacyl and alkenylacyl species have the same m/z value as molecular-related ions and fragment ions, thus, direct acid hydrolysis analysis was performed to identify alkylacyl and alkenylacyl species, and then the RPLC–LTQ Orbitrap method was applied. As a result, 290 species from mouse liver and 248 species from mouse brain were identified within six different classes of phospholipid, only those in manually detected and confirmed. Most of all manually detected mass peaks were also automatically detected by “Lipid Search”. Adding to differences in molecular species in different classes of phospholipids, many characteristic differences in molecular species were detected in mouse liver and brain. More variable number of saturated and monounsaturated fatty acid-containing molecular species were detected in mouse brain than liver.     

Acceptable range of speech level in noisy sound fields for young adults and elderly persons

The acceptable range of speech level as a function of background noise level was investigated on the basis of word intelligibility scores and listening difficulty ratings. In the present study, the acceptable range is defined as the range that maximizes word intelligibility scores and simultaneously does not cause a significant increase in listening difficulty ratings from the minimum ratings. Listening tests with young adult and elderly listeners demonstrated the following. (1) The acceptable range of speech level for elderly listeners overlapped that for young listeners. (2) The lower limit of the acceptable speech level for both young and elderly listeners was 65 dB (A-weighted) for noise levels of 40 and 45 dB (A-weighted), a level with a speech-to-noise ratio of +15 dB for noise levels of 50 and 55 dB, and a level with a speech-to-noise ratio of +10 dB for noise levels from 60 to 70 dB. (3) The upper limit of the acceptable speech level for both young and elderly listeners was 80 dB for noise levels from 40 to 55 dB and 85 dB or above for noise levels from 55 to 70 dB.     

Gasification characteristics of woody biomass in the packed bed reactor

Gasification technology is recognized as one of the possibilities for utilizing biomass effectively. This study focused on woody biomass gasification fundamentals, using a bench-scale packed-bed reactor. In this experiment, pellets of black pine were gasified, using air as the oxidizing agent. Gasification tests were carried out under both updraft and downdraft conditions. Temperature distributions and compositions of syngas inside the gasifier were continuously monitored during gasification experiments at several ports on the wall of the reactor. The syngas at the exit of the gasifier was also sampled to estimate the amount of tar. Lower heating values of the syngas under updraft and downdraft conditions were 4.8 and 3.8 MJ/m³N, respectively. It was easier to control the height of the packed bed under the downdraft condition than under the updraft condition. Under the updraft condition, a bridging phenomenon occurred. Tar generation under the downdraft condition was lower than that under the updraft condition. This is because tar passes through a partial combustion zone or higher temperature zone in the downdraft gasifier.     

Comparison of reactivity on step and terrace sites of Pd (3 3 2) surface for the dissociative adsorption of hydrogen: A quantum chemical molecular dynamics study

The notion of “active sites” is fundamental to heterogeneous catalysis. However, the exact nature of the active sites, and hence the mechanism by which they act, are still largely a matter of speculation. In this study, we have presented a systematic quantum chemical molecular dynamics (QCMD) calculations for the interaction of hydrogen on different step and terrace sites of the Pd (3 3 2) surface. Finally the dissociative adsorption of hydrogen on step and terrace as well as the influence of surface hydrogen vacancy for the dissociative adsorption of hydrogen has been investigated through QCMD. This is a state-of-the-art method for calculating the interaction of atoms and molecules with metal surfaces. It is found that fully hydrogen covered (saturated) step sites can dissociate hydrogen moderately and that a monovacancy surface is suitable for significant dissociative adsorption of hydrogen. However in terrace site of the surface we have found that dissociation of hydrogen takes place only on Pd sites where the metal atom is not bound to any pre-adsorbed hydrogen atoms. Furthermore, from the molecular dynamics and electronic structure calculations, we identify a number of consequences for the interpretation and modeling of diffusion experiments demonstrating the coverage and directional dependence of atomic hydrogen diffusion on stepped palladium surface.     

Procyanidins are potent inhibitors of LOX-1: a new player in the French Paradox

Lectin-like oxidized LDL receptor-1 (LOX-1) is an endothelial receptor for oxidized LDL (oxLDL) and plays multiple roles in the development of cardiovascular diseases. We screened more than 400 foodstuff extracts for identifying materials that inhibit oxLDL binding to LOX-1. Results showed that 52 extracts inhibited LOX-1 by more than 70% in cell-free assays. Subsequent cell-based assays revealed that a variety of foodstuffs known to be rich in procyanidins such as grape seed extracts and apple polyphenols, potently inhibited oxLDL uptake in Chinese hamster ovary (CHO) cells expressing LOX-1. Indeed, purified procyanidins significantly inhibited oxLDL binding to LOX-1 while other ingredients of apple polyphenols did not. Moreover, chronic administration of oligomeric procyanidins suppressed lipid accumulation in vascular wall in hypertensive rats fed with high fat diet. These results suggest that procyanidins are LOX-1 inhibitors and LOX-1 inhibition might be a possible underlying mechanism of the well-known vascular protective effects of red wine, the French Paradox.