Two-Step Synthesis of trans-2-Arylcyclopropane Carboxylates with 98–100 % ee by the Use of a Phosphazene Base

Only the axial diastereomer of sulfonium salts 2 are formed upon alkylation of 1 . Deprotonation of 2 results in ylides, which allow the highly enantioselective cyclopropanation of Michael systems. The chiral auxiliary 1 is recovered and can be reused.     

Influence of copolymer composition of polyestercarbonate on miscibility with poly(butylene terephthalate)

Blends of poly(butylene terephthalate) (PBT) and polyestercarbonate (PEC), copolyesters consisting of polycarbonate (PC) and polyarylate (PAr), have been studied by thermal analysis to determine miscibility. The PBT blends with PAr and PEC containing 30 wt % of carbonate unit or less appeared to be miscible, and the tendency for stable single‐phase was observed to decrease as the content of carbonate unit in PEC copolymer increased. As determined with the crystalline phase behavior, the miscibility of PEC with PBT appeared to have a maximum around 10 ∼ 30 wt % of carbonate content in PEC copolymer, and this result was attributed to the internal repulsion effect between ester and carbonate repeating units in PEC copolymer. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 803–811, 2000     

Proteome analysis of human liver tumor tissue by two-dimensional gel electrophoresis and matrix assisted laser desorption/ionization-mass spectrometry for identification of disease-related proteins

Hepatocellular carcinoma (HCC) is a common malignancy worldwide and is a leading cause of death. To contribute to the development and improvement of molecular markers for diagnostics and prognostics and of therapeutic targets for the disease, we have largely expanded the currently available human liver tissue maps and studied the differential expression of proteins in normal and cancer tissues. Reference two-dimensional electrophoresis (2-DE) maps of human liver tumor tissue include labeled 2-DE images for total homogenate and soluble fraction separated on pH 3-10 gels, and also images for soluble fraction separated on pH 4-7 and pH 6-9 gels for a more detailed map. Proteins were separated in the first dimension by isoelectric focusing on immobilized pH gradient (IPG) strips, and by 7.5-17.5% gradient sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) gels in the second dimension. Protein identification was done by peptide mass fingerprinting with delayed extraction-matrix assisted laser desorption/ionization-time of flight-mass spectrometry (DE-MALDI-TOF-MS). In total, 212 protein spots (117 spots in pH 4-7 map and 95 spots in pH 6-9) corresponding to 127 different polypeptide chains were identified. In the next step, we analyzed the differential protein expression of liver tumor samples, to find out candidates for liver cancer-associated proteins. Matched pairs of tissues from 11 liver cancer patients were analyzed for their 2-DE profiles. Protein expression was comparatively analyzed by use of image analysis software. Proteins whose expression levels were different by more than three-fold in at least 30% (four) of the patients were further analyzed. Numbers of protein spots overexpressed or underexpressed in tumor tissues as compared with nontumorous regions were 9 and 28, respectively. Among these 37 spots, 1 overexpressed and 15 underexpressed spots, corresponding to 11 proteins, were identified. The physiological significance of the differential expressions is discussed.     

Titanium K-edge absorption structure in Ti1−x NbxO2

The fine structure in the titanium x-ray K-edge absorption has been measured in Ti_1−x Nb_xO₂ mixed dioxides (x=0–0.1) with rutile structure in a laboratory-type spectrometer by total electron quantum-yield measurement. The position of the XANES lines is shown to be in good agreement with classical x-ray absorption spectra obtained in transmission. The structure and main features of the XANES spectra, including the effects of impurities and manyelectron excitations, are discussed. It is suggested that the intensity of the B peak characteristic of the titanium K edge depends on the Nb concentration and correlates with the charge state of titanium ions. Fiz. Tverd. Tela (St. Petersburg) 41, 894–896 (May 1999)     

Ligand Sensitized Flourometric Determination of Dysprosium(III) Ion Using Terephthalic Acid

Several trivalent lanthanide ions are known to exhibit excellent luminescence characteristics when they are coordinated with appropriate organic ligands. Various analytical methods have been developed to determine lanthanide ions or organic compounds by taking advantage of these luminescence characteristics. The luminescence enhancement of the lanthanide ions by complexation with organic ligands has been explained on the basis of a ligand to metal energy transfer process.     

Coassembled Nanoparticles Composed of Functionalized Mesoporous Silica and Pillar[5]arene-Appended Gold Nanoparticles as Mitochondrial-Selective Dual-Drug Carriers

Coassembled nanoparticles composed of functionalized mesoporous silica and pillar[5]arene-appended Au nanoparticles obtained through the formation of a host–guest complex are designed and synthesized as a mitochondrial-selective dual-drug delivery system. A pyridinium-based ligand and fluorescein isothiocyanate are immobilized onto mesoporous silica to act as the mitochondria-targeting ligand and fluorescence tracker, respectively, of a material dubbed NP-3. Carboxylated pillar[5]arene-capped Au nanoparticles (CP-AuNPs) are fabricated by the templated reduction of Au³⁺. Interestingly, coassembled nanoparticles (NP-1) composed of doxorubicin (DOX) loaded NP-3 and CP-AuNPs are then prepared via the formation of a host–guest complex between the pyridinium-based ligand of NP-3 and the pillar[5]arene of CP-AuNPs. To demonstrate the effectiveness of NP-2 and NP-1 as mitochondrial targeting drug delivery systems, DOX and F16 are employed as model drugs. These drugs loaded onto NP-2 and CP-AuNPs, respectively, are selectively delivered to mitochondria, indicating the usefulness of NP-2 and CP-AuNPs as mitochondrial-specific drug-delivery carriers in cancer cells. More interestingly, the use of NP-1 is also associated with the selective accumulation of DOX and F16 in mitochondria. The selective mitochondrial-targeting of NP-1 is possible by NP-2 and F16 exposed to the cytoplasm, allowing the codelivery of the two drugs to the mitochondria.     

Surface modification of polyurethane for enhanced blood compatibility

Surfaces of commercial polyurethanes (PUs) were modified by poly(ethylene oxide) (PEO) grafting and/or heparin immobilization or sulfonation to investigate the effect to antithrombogenicity. The hydrophilicity of the modified PUs surface was significantly increased. All the PEO-grafted PU surfaces displayed very little platelet adhesion and activation. The coupled heparin or sulfonate at the end of PEO exhibited anticoagulant activity to extend APTT. Lowering in vitro platelet adhesion of modified PUs led to a prolongation in the ex vivo occlusion time. In particular, the sulfonated PU-PEO surface showed the most enhanced blood compatibility due to the synergistic effects of PEO and SO₃ groups.     

Hepatoprotective Potential of Malaysian Medicinal Plants: A Review on Phytochemicals,Oxidative Stress,and Antioxidant Mechanisms

Hepatotoxicity is a major global public health concern. Despite advances in modern medicine, the demerits of chemically prepared drugs outweigh their merits. In addition, the treatment of liver diseases based on modern medical principles has been found to produce several undesired side effects. Therefore, the exploration of medicinal plants has gained worldwide attention for treating various diseases, including liver diseases, owing to their potential efficacy and cost effectiveness. Several plants, including Andrographis paniculata, Bauhinia purpurea, Commelina nudiflora, Dillenia suffruticosa, Elaeis guineensis, Lygodium microphyllum, and Nephrolepis biserrata, have been reported with hepatoprotection. Moreover, these plants have been shown to play a vital role in ameliorating cellular damage because they contain several phytochemicals, including alkaloids, saponins, flavonoids, tannins, terpenoids, steroids, polyphenols, and diterpenoid lactones. The following antioxidant, anti-inflammatory, immunomodulatory, and hepatoprotective compounds have been found in these plants: andrographolide, rosmarinic acid, phenol, eugenol, 9,12-octadecadienoic, n-hexadecanoic acid, dihydroxy dimethoxy flavone, sitosterol, demethoxycurcumin, quercetin, linoleic acid, stigmasterol, kojic acid, indole-2-one, α-terpinol, linalool, kaempferol, catechin, ellagic acid, and oleanolic acid. This paper aimed to provide an in-depth review of in vivo studies on Malaysian medicinal plants possessing hepatoprotective properties, phytochemical ingredients, and antioxidant mechanisms, with an emphasis on the species proven particularly useful for treating hepatic disorders.     

Effects of Sphingomyelin-Containing Milk Phospholipids on Skin Hydration in UVB-Exposed Hairless Mice

Reactive oxygen species (ROS) generated by ultraviolet (UV) exposure cause skin barrier dysfunction, which leads to dry skin. In this study, the skin moisturizing effect of sphingomyelin-containing milk phospholipids in UV-induced hairless mice was evaluated. Hairless mice were irradiated with UVB for eight weeks, and milk phospholipids (50, 100, and 150 mg/kg) were administered daily. Milk phospholipids suppressed UV-induced increase in erythema and skin thickness, decreased transepidermal water loss, and increased skin moisture. Milk phospholipids increased the expression of filaggrin, involucrin, and aquaporin3 (AQP3), which are skin moisture-related factors. Additionally, hyaluronic acid (HA) content in the skin tissue was maintained by regulating the expression of HA synthesis- and degradation-related enzymes. Milk phospholipids alleviated UV-induced decrease in the expression of the antioxidant enzymes superoxidase dismutase1 and 2, catalase, and glutathione peroxidase1. Moreover, ROS levels were reduced by regulating heme oxygenase-1 (HO-1), an ROS regulator, through milk phospholipid-mediated activation of nuclear factor erythroid-2-related factor 2 (Nrf2). Collectively, sphingomyelin-containing milk phospholipids contributed to moisturizing the skin by maintaining HA content and reducing ROS levels in UVB-irradiated hairless mice, thereby, minimizing damage to the skin barrier caused by photoaging.