Synthesis of the Right-Side Structure of Type B Physalins.

We present a full account of our synthetic studies on the racemic DEFGH-ring moiety of physalins, featuring domino ring transformation of a tricyclic key intermediate. We also report the results of a detailed mechanistic examination of the domino ring transformation, as well as a reoptimization of the 2,3-Wittig rearrangement and methylation steps. Furthermore, we have newly established a method for the preparation of an optically active synthetic intermediate by enzymatic kinetic resolution. Our work provides access to both natural and nonnatural right-side physalin structures.

[Factors related to the long-term prognosis of home-based medical care subjects].

AIM: The purpose of this study is to identify the factors affecting long-term prognosis of home-based medical care subjects. METHODS: We evaluated 290 subjects, who received home-based medical care between January 2012 and May 2015. We evaluated several aspects of the activities of daily living, such as the ability to walk, use of the toilet, self-feeding and self-administering of medications, as well as their cognition, activities, and abilities to communicate. The influence of these parameters on major adverse cardiovascular cerebrovascular events, non-cardiovascular, cerebrovascular events and the incidence of death was evaluated. RESULTS: The mean age of the subjects was 83 years old and 38% of them were male: dementia or previous cerebral infarction was their main diagnosis. They required assistance for almost all activities of daily living except for feeding. Primary health concerns included 103 (37.0%) subjects had non-cardiovascular, cerebrovascular events, 63 subjects (21.7%) had pneumonia, and 48 subjects (16.6%) suffered major adverse cardiovascular cerebrovascular events, including 22 subjects (7.6%) with congestive heart failure. Sixty-one subjects (21.0%) died. The activities of daily living and cognition correlated strongly with non-cardiovascular, cerebrovascular events and death. CONCLUSION: Our results indicated the activities of daily living and cognition strongly influence the occurrence of non-cardiovascular, cerebrovascular events and death in subjects receiving home-based medical care. Therefore, intervention should be targeted at improving these subjects' abilities to perform activities of daily living.

An oxyhydride of BaTiO3 exhibiting hydride exchange and electronic conductivity.

In oxides, the substitution of non-oxide anions (F(-),S(2-),N(3-) and so on) for oxide introduces many properties, but the least commonly encountered substitution is where the hydride anion (H(-)) replaces oxygen to form an oxyhydride. Only a handful of oxyhydrides have been reported, mainly with electropositive main group elements or as layered cobalt oxides with unusually low oxidation states. Here, we present an oxyhydride of the perhaps most well-known perovskite, BaTiO(3), as an O(2-)/H(-) solid solution with hydride concentrations up to 20% of the anion sites. BaTiO(3-x)H(x) is electronically conducting, and stable in air and water at ambient conditions. Furthermore, the hydride species is exchangeable with hydrogen gas at 400 °C. Such an exchange implies diffusion of hydride, and interesting diffusion mechanisms specific to hydrogen may be at play. Moreover, such a labile anion in an oxide framework should be useful in further expanding the mixed-anion chemistry of the solid state.

Synthesis of DFGH-Ring Derivatives of Physalins via One-Pot Construction of GH-Ring and Evaluation of Their NF-κB-Inhibitory Activity.

We designed and synthesized a series of derivatives containing the right-side DFGH-ring structure of physalin-type natural products, decorated with a hydrophobic substituent. The synthetic scheme utilizes a highly efficient, one-pot protocol for simultaneous construction of the GH-ring system, promoted by HF/pyridine. Among the compounds synthesized, 5d inhibited TNF-α-stimulated NF-κB activation with similar potency to physalin B.

Quantitative Determination of NTA and Other Chelating Agents in Detergents by Potentiometric Titration with Copper Ion Selective Electrode.

Quantitative analysis of nitrilotriacetate (NTA) in detergents by titration with Cu2+ solution using a copper ion selective electrode was achieved. This method tolerates a wide range of pH and ingredients in detergents. In addition to NTA, other chelating agents, having relatively lower stability constants toward Cu2+, were also qualified with sufficient accuracy by this analytical method for model detergent formulations. The titration process was automated by automatic titrating systems available commercially.

Comparative Characterization of the Leaf Tissue of Physalis alkekengi and Physalis peruviana Using RNA-seq and Metabolite Profiling.

The genus Physalis in the Solanaceae family contains several species of benefit to humans. Examples include P. alkekengi (Chinese-lantern plant, hôzuki in Japanese) used for medicinal and for decorative purposes, and P. peruviana, also known as Cape gooseberry, which bears an edible, vitamin-rich fruit. Members of the Physalis genus are a valuable resource for phytochemicals needed for the development of medicines and functional foods. To fully utilize the potential of these phytochemicals we need to understand their biosynthesis, and for this we need genomic data, especially comprehensive transcriptome datasets for gene discovery. We report the de novo assembly of the transcriptome from leaves of P. alkekengi and P. peruviana using Illumina RNA-seq technologies. We identified 75,221 unigenes in P. alkekengi and 54,513 in P. peruviana. All unigenes were annotated with gene ontology (GO), Enzyme Commission (EC) numbers, and pathway information from the Kyoto Encyclopedia of Genes and Genomes (KEGG). We classified unigenes encoding enzyme candidates putatively involved in the secondary metabolism and identified more than one unigenes for each step in terpenoid backbone- and steroid biosynthesis in P. alkekengi and P. peruviana. To measure the variability of the withanolides including physalins and provide insights into their chemical diversity in Physalis, we also analyzed the metabolite content in leaves of P. alkekengi and P. peruviana at five different developmental stages by liquid chromatography-mass spectrometry. We discuss that comprehensive transcriptome approaches within a family can yield a clue for gene discovery in Physalis and provide insights into their complex chemical diversity. The transcriptome information we submit here will serve as an important public resource for further studies of the specialized metabolism of Physalis species.

Mass spectroscopic approach to amino acids formation processes by UV irradiation to simple organic molecules in aqueous solution.

We have studied amino acid formation by UV (193 nm) irradiation to organic molecules (amines, alcohols and amides) in aqueous solution. Among several types of detected amino acids, small aliphatic amino acids (Gly and alpha-, beta-Ala and alpha-, beta-, gamma-ABA) were quantitatively identified. Among these small aliphatic amino acids, certain amino acids were formed in its free form, even before hydrolysis, contrary to the results of UV irradiation to a gas mixture of CO, NH3, and H2O, where amino acids were hardly detected before hydrolysis. The species distribution of identified amino acids showed a dependence on the starting organic molecules, and also on the presence of ammonia. The formation processes of the identified small aliphatic amino acids were investigated with the aid of electrospray ionization (ESI) MS and MS/MS measurements of photoproducts. Possible formation processes of these amino acid precursors from each starting molecules are proposed. By identifying the amino acid precursor, which has a chiral carbon atom, a new possibility is suggested for asymmetric photosynthesis of amino acid from achiral organic molecules.

Contribution of Cage-Shaped Structure of Physalins to Their Mode of Action in Inhibition of NF-κB Activation.

A library of oxygenated natural steroids, including physalins, withanolides, and perulactones, coupled with the synthetic cage-shaped right-side structure of type B physalins, was constructed. SAR studies for inhibition of NF-κB activation showed the importance of both the B-ring and the oxygenated right-side partial structure. The 5ß,6ß-epoxy derivatives of both physalins and withanolides showed similar profiles of inhibition of NF-κB activation and appeared to act on NF-κB signaling via inhibition of phosphorylation and degradation of IκBα. In contrast, type B physalins with C5-C6 olefin functionality inhibited nuclear translocation and DNA binding of RelA/p50 protein dimer, which lie downstream of IκBα degradation, although withanolides having the same AB-ring functionality did not. These results indicated that the right-side partial structure of these steroids influences their mode of action.

Kinetically controlled one-pot formation of DEFGH-rings of type B physalins through domino-type transformations.

The characteristic DEFGH-ring system of type B physalins has been synthesized by means of a one-pot procedure incorporating domino-type ring transformations. Unexpectedly, we found that introduction of an α-hydroxyester functionality at C17 in ring E allowed the key 7-endo oxy-Michael reaction to proceed. Originally this was thought to be an unfavored process. This afforded the desired caged ring system to be formed in a kinetically controlled manner. Consecutive treatment with AcOH at 100 °C furnished the DEFGH-ring system in one pot.

Interfacial-specific chemiluminescence at Liqud/liquid interfaces or at O/W emulsions containing lucigenin in oil phase.

The enhanced effect of chemiluminescence (CL) of lucigenin (Luc(2+)) at a flat liquid/liquid interface and at O/W emulsions was demonstrated. The CL was emitted when Luc(2+) was transferred from an organic phase to an aqueous one containing NaOH and H(2)O(2). The CL intensity and emission spectrum depended strongly on the kind of organic solvent. We attempted to apply the CL reaction of Luc(2+) in the O/W emulsion system to the analysis of H(2)O(2). The available analytical conditions were discussed from the aspects of the kind of organic solvent, the reaction time and wavelength detected.

Refraction contrast 11x-magnified X-ray imaging of large objects by MIRRORCLE-type table-top synchrotron.

The high-quality aspects of magnified X-ray images recorded using MIRRORCLE-6X are reported. MIRRORCLE-6X is inherently suitable for hard X-ray imaging owing to its magnified projection X-ray imaging, micrometre-size X-ray source point, wide radiation emission angle, X-ray spectrum ranging from 10 keV to 6 MeV, natural refraction contrast imaging and high flux output. Images produced with 11x geometrical magnification display a sharply enhanced edge effect when generated using a 25 microm rod electron target. Image contrast is enhanced 2x owing to refraction when compared with absorption contrast images. An imitation tumour implanted in a human chest phantom was made clearly visible by using edge enhancement on images. Soft tissue becomes highly visible as a natural consequence of refraction contrast when using hard X-rays for imaging. The authors believe that novel imaging provided by MIRRORCLE makes it a superior instrument for medical diagnosis.

Synthesis, structure, and reactivity of a eta(3)-1-hydroxyallyl complex: protonation of an alpha,beta-unsaturated carbonyl compound bound to palladium(0) and platinum(0).

The direct addition of a proton to a carbonyl oxygen in an eta2-enone complex of palladium and platinum led to the quantitative formation of eta3-1-hydroxyallyl complexes of palladium and platinum, of which X-ray diffraction analysis showed typical eta3-allyl structure.

Palladium/Me(3)SiOTf-catalyzed bis-silylation of alpha,beta-unsaturated carbonyl compounds without involving oxidative addition of disilane.

In the presence of a catalytic amount of Me(3)SiOTf and palladium(0), the addition of disilane to alpha,beta-unsaturated carbonyl compounds proceeds under very mild conditions via eta(3)-siloxyallylpalladium generated by the reaction of enone, enal, or aromatic aldehyde with palladium and Me(3)SiOTf.