Poly(p-tert-butoxycarbonyloxystyrene): a convenient precursor to p-hydroxystyrene resins

An efficient synthetic route to pure, high molecular weight poly(p-hydroxystyrene) is reported. The route involves synthesis of a new monomer, p-tert-butoxycarbonyloxystyrene, polymerization by radical initiation or by cationic initiation in liquid SO₂, followed by thermolysis or acidolysis of the tert-butoxycarbonyl protecting group. Porous, crosslinked resin beads containing the nucleophilic, phenol pendant group have been prepared in a similar fashion from the precursor terpolymer of p-tert-butoxycarbonyloxystyrene, styrene and divinylbenzene. The utility of this resin for solid-phase synthesis has been demonstrated.     

Selective synthesis of isobutene trimers and hexamers with oxo acid catalysts

The reaction of isobutene (IB) with its dimers (IB₂) catalyzed by CF₃SO₃H yielded isobutene trimers (IB₃) in high yield in nonpolar solvents at 0°C. The initial feed of isobutene, in the presence of equimolar IB₂ or more, was selectively converted into IB₃ without loss or accumulation of IB₂. After complete consumption of the isobutene, however, the remaining IB₂ rapidly dimerized to isobutene tetramers (IB₄). ¹³C-NMR analysis of the products showed that the IB₃ was formed via addition of the t-butyl cation (protonated isobutene to 2,4,4-trimethyl-1-pentene (an IB₂ isomer); the trimer fraction was free from isomers arising from addition of the t-butyl cation to 2,4,4-trimethyl-2-pentene (another IB₂ isomer) or addition of the IB₂ cation to isobutene. The IB₃ thus obtained was further oligomerized with CF₃SO₃H catalyst in nonpolar media in the range of 0 to ?25°C to give a mixture of IB₅, IB₆, and IB₇ in high yield. With EtAlCl₂ as catalyst, reaction of isobutene with IB₂ and oligomerization of IB₃ both resulted in products with a broad molecular weight distribution containing higher oligomers and complex hydrocarbons formed via cracking of the intermediate carbocations.     

Suppression of inducible nitric oxide synthase expression and amelioration of lipopolysaccharide-induced liver injury by polyphenolic compounds in Eucalyptus globulus leaf extract

Eucalyptus leaf extract (ELE) is rich in hydrolyzable tannins. We examined the effects of ELE and its constituents on lipopolysaccharide (LPS)-induced liver injury in mice. Mice fed a diet supplemented with 1% ELE were intraperitoneally administered LPS. Six hours later, the serum alanine aminotransferase (ALT) and aspartate aminotransferase (AST) activities were significantly lower in the ELE-supplemented mice than in the controls; LPS-induced hepatic inducible nitric oxide synthase (iNOS) expression was also suppressed. ELE lowered LPS-stimulated iNOS expression in cultured RAW 264.7 macrophages. Furthermore, the aglycones of hydrolyzable tannins, gallic acid (GA) and ellagic acid (EA), inhibited iNOS induction to a greater extent than did ELE (15-fold higher). When mice were fed a 1% GA or EA diet, the increase in the serum ALT and AST activities and hepatic iNOS expression in response to the LPS challenge were significantly attenuated. Thus, hydrolyzable tannins in ELE ameliorate LPS-induced liver injury.     

Immunomodulatory effect of mushrooms on cytotoxic activity and cytokine production of intestinal lamina propria leukocytes does not necessarily depend on β-glucan contents

We evaluated the effects of seven mushroom extracts (Grifola frondosa, Pholiota nameko, Panellus serotinus, Hypsizygus marmoreus, Pleurotus cornucopiae, Armillaria mellea, and Flammulina velutipes) on cytotoxic activity and cytokine production of lamina propria leukocytes (LPLs) isolated from rat small (S) and large (L) intestinal mucosa. Boiling water extracts from seven species of mushrooms showed no direct cytotoxicity against the YAC-1 target cells. However, prominent increases of cytotoxicity were observed in S- and L-LPLs co-cultured with P. serotinus extract. Cytokine production (TNFα, IFNγ, IL-12 p70, and IL-4) of S- and L-LPLs was stimulated in response to P. cornucopiae extract. Mushroom extracts contributed to target cell adhesion and/or cytokine production in the effector cells. The promotion of cytotoxic activity in S- and L-LPLs was not necessarily related to β-glucan content of the mushroom.     

Breeding of a high tyrosol‐producing sake yeast by isolation of an ethanol‐resistant mutant from a trp3 mutant

A novel breeding strategy for a high tyrosol‐producing sake yeast was developed by isolating an ethanol‐resistant mutant from a tryptophan auxotrophic mutant of a sake brewery yeast. Since tyrosol has antioxidant, cardioprotective and taste‐sharpening effects, increasing the tyrosol level of alcohol beverages could be beneficial in alcohol production. Since the transporters of aromatic amino acids are degraded by several stresses and mutants defective in the synthesis of aromatic amino acids are sensitive to ethanol, it was hypothesized that the degradation of these transporters should be inhibited in ethanol resistant mutants isolated from the auxotrophic mutants of aromatic amino acids, and that the uptake of aromatic amino acids would be increased in the mutants. Consistent with this hypothesis, sake was brewed with the ethanol‐resistant mutant of a tryptophan auxotrophic mutant and the sake was found to contain a lesser content of tyrosine and a higher content of tyrosol relative to the sake brewed with the parental strains. The taste of the sake brewed with the mutant strain could be discriminated from the sake brewed with the parental strains, probably because of the altered concentrations of tyrosol and certain amino acids and organic acids. The results suggest that combining the isolation of an ethanol‐resistant mutant and an auxotrophic mutant is an effective method to breed a brewing strain with a modified metabolism of these substances. Copyright © 2012 The Institute of Brewing & Distilling     

Polyphenols Extracted from Black Tea (Camellia sinensis) Residue by Hot‐Compressed Water and Their Inhibitory Effect on Pancreatic Lipase in vitro

Abstract: Polyphenols, retained in black tea wastes following the commercial production of tea beverages, represent an underutilized resource. The purpose of this study was to investigate the potential use of hot‐compressed water (HCW) for the extraction of pancreatic lipase‐inhibiting polyphenols from black tea residues. Black tea residues were treated with HCW at 10 °C intervals, from 100 to 200 °C. The resulting extracts were analyzed using high‐performance liquid chromatography‐mass spectrometry and assayed to determine their inhibitory effect on pancreatic lipase activity in vitro. Four theaflavins (TF), 5 catechins, 2 quercetin glycosides, quinic acid, gallic acid, and caffeine were identified. The total polyphenol content of extracts increased with increasing temperature but lipase inhibitors (TF, theaflavin 3‐O‐gallate, theaflavin 3′‐O‐gallate, theaflavin 3,3′‐O‐gallate, epigallocatechin gallate, and epicatechin gallate) decreased over 150 °C. All extracts inhibited pancreatic lipase but extracts obtained at 100 to 140 °C showed the greatest lipase inhibition (IC₅₀s of 0.9 to 1.3 μg/mL), consistent with the optimal extraction of TFs and catechins except catechin by HCW between 130 and 150 °C. HCW can be used to extract pancreatic lipase‐inhibiting polyphenols from black tea waste. These extracts have potential uses, as dietary supplements and medications, for the prevention and treatment of obesity. Practical Application: Active forms of lipase inhibitors can be recovered from black tea residues. They could be used as dietary supplements or medications.     

Effects of Phosphoryl Oligosaccharides of Calcium (POs-Ca) on Mycelial Growth and Fruiting Body Development of the Edible Mushroom,Pleurotus ostreatus

Phosphoryl oligosaccharides of calcium (POs-Ca) is a calcium salt of phosphoryl maltooligosaccharides made from potato starch. POs-Ca is highly water-soluble and can supply both the calcium ion and acidic oligosaccharides in an aqueous solution. In this study, we investigated the effects of POs-Ca on the mycelial growth and fruiting body yield of Pleurotus ostreatus , which is one of the most widely cultivated edible mushrooms in the world. We cultivated the mushroom using both potato dextrose agar (PDA) medium and sawdust-based medium, with added calcium salts. The addition of POs-Ca into the PDA medium with a calcium concentration of 10 mg increased mycelial growth significantly ( p < 0.05, vs . control). POs-Ca addition to the sawdust-based medium at concentrations of 1.0 to 3.0 g/100 g medium increased the amount of calcium in the fruiting bodies but did not affect the length of the cultivation period or the weight of the fruiting body. The calcium content in the fruiting body increased 12-fold when compared to the control. On the other hand, neither the CaHPO ₄ ･2H ₂ O group nor the CaHPO ₄ ･2H ₂ O with oligosaccharides group showed changes in the calcium content of the fruiting bodies. Our results indicate that the use of POs-Ca in mushroom cultivation allows for the possibility of developing new functional foods like calcium-enriched edible mushrooms. This is the first report describing the effects of POs-Ca on mushroom cultivation.