Structural analyses of (1->3),(1->4)-β-D-glucan of oats and barley

The structures of (1→3),(1→4)-β-D-glucans of oat bran, whole-grain oats and barley and processed foods were analysed. Various methods of hydrolysis of β-glucan, the content of insoluble fibre of whole grains of oats and barley and the solution behaviour of oat and barley β-glucans were studied. The isolated soluble β-glucans of oat bran and whole-grain oats and barley were hydrolysed with lichenase, an enzyme specific for (1→3),(1→4)-β-D-β-glucans. The amounts of oligosaccharides produced from bran were analysed with capillary electrophoresis and those from whole-grains with high-performance anion-exchange chromatography with pulse-amperometric detection. The main products were 3-O-β-cellobiosyl-D-glucose and 3-O-β-cellotriosyl-D-glucose, the oligosaccharides which have a degree of polymerisation denoted by DP3 and DP4. Small differences were detected between soluble and insoluble β-glucans and also between β-glucans of oats and barley. These differences can only be seen in the DP3:DP4 ratio which was higher for barley than for oat and also higher for insoluble than for soluble β-glucan. A greater proportion of barley β-glucan remained insoluble than of oat β-glucan. The molar masses of soluble β-glucans of oats and barley were the same as were those of insoluble β-glucans of oats and barley. To analyse the effects of cooking, baking, fermentation and drying, β-glucan was isolated from porridge, bread and fermentate and also from their starting materials. More β-glucan was released after cooking and less after baking. Drying decreased the extractability for bread and fermentate but increased it for porridge. Different hydrolysis methods of β-glucan were compared. Acid hydrolysis and the modified AOAC method gave similar results. The results of hydrolysis with lichenase gave higher recoveries than the other two. The combination of lichenase hydrolysis and high-performance anion-exchange chromatography with pulse-amperometric detection was found best for the analysis of β-glucan content. The content of insoluble fibre was higher for barley than for oats and the amount of β-glucan in the insoluble fibre fraction was higher for oats than for barley. The flow properties of both water and aqueous cuoxam solutions of oat and barley β-glucans were studied. Shear thinning was stronger for the water solutions of oat β-glucan than for barley β-glucan. In aqueous cuoxam shear thinning was not observed at the same concentration as in water but only with high concentration solutions. Then the viscosity of barley β-glucan was slightly higher than that of oat β-glucan. The oscillatory measurements showed that the crossover point of the G´ and G´´ curves was much lower for barley β-glucan than for oat β-glucan indicating a higher tendency towards solid-like behaviour for barley β-glucan than for oat β-glucan.

Photolysis of the dithiolactone 4-isopropylidene-3,3-dimethyl-1-thietan-2-thione; a Norrish type I reaction

The dithiolactone (1) upon excitation gives the dithione (2) in cyclohexane and other aprotic solvents and a 1 : 1 adduct in hydroxylic solvents from an n* excited singlet state via an -cleavage process.

Regulation of oxidative-stress responsive genes by arecoline in human keratinocytes

Background and Objective: Arecoline, an arecanut alkaloid present in the saliva of betel quid chewers, has been implicated in the pathogenesis of a variety of inflammatory oral diseases, including oral submucous fibrosis and periodontitis. To understand the molecular b asis of arecoline action in epithelial changes associated with these diseases, we investigated the effects of arecoline on human keratinocytes with respect to cell growth regulation and the expression of stress-responsive genes.Material and Methods:Human keratinocyte cells (of the HaCaT cell line) were treated with arecoline, following which cell viability was assessed using the Trypan Blue dye-exclusion assay, cell growth and proliferation were analyzed using the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) and 5-bromo-2-deoxyuridine incorporation assays, cell cycle arrest and generation of reactive oxygen species were examined using flow cytometry, and gene expression changes were investigated using the reverse transcription-polymerase chain reaction technique. The role of oxidative stress, muscarinic acetylcholine receptor and mitogen-activated protein kinase (MAPK) pathways were studied using specific inhibitors. Western blot analysis was performed to study p38 MAPK activation.Results:Arecoline induced the generation of reactive oxygen species and cell cycle arrest at the G1/G0 phase in HaCaT cells without affecting the expression of p21/Cip1. Arecoline-induced epithelial cell death at higher concentrations was caused by oxidative trauma without eliciting apoptosis. Sublethal concentrations of arecoline upregulated the expression of the following stress-responsive genes: heme oxygenase-1; ferritin light chain; glucose-6-phosphate dehydrogenase; glutamate-cysteine ligase catalytic subunit; and glutathione reductase.Additionally, there was a dose-dependent induction of interleukin-1alfa mRNA by arecoline via oxidative stress and p38 MAPK activation. Conclusion:our data highlight the role of oxidative stress in arecoline-mediated cell death, gene regulation and inflammatory processes in human keratinocytes.

Intermolecular charge-transfer complexes of macrocyclic polyethers with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone

The interactions of benzo-15-crown-5, dibenzo-18-crown-6, and dibenzo-24-crown-8 with 2,3-dichloro-5,6-dicyano- 1,4-benzoquinone have been studied in methylene chloride by using spectroscopic methods. These crown ethers from 1:l molecular complexes with the acceptor. The magnitudes of association constants and thermodynamic parameters of complexation are indicative of cooperative interaction of oxygens with the acceptor.

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Oxidation of Abel's ketone and similar spiroketones with 2,3-dichloro-5,6-dicyano-1,4- benzoquinone (DDQ). Synthesis of novel tropone derivatives

The structure of the novel product obtained from the oxidation of Abel's ketone (1a) and similar spiroketones (1b–d) with 2, 3-dichloro-5, 6-dicyano-1,4-benzoquinone has been determined on basis of spectral data (i.r., n.m.r., and mass)

Unusual products of oxidation with Cr(VI) of methyl 5-methyl-7-methoxy-8-isopropyl-3,4-2-naphthoate

Abstract is not available.

Studies in metal-ammonia reduction. Part 4. Reduction and reductive methylation of 7-methoxy-3,4-dihydrophenanthren-1(2H)-one and 7-methoxy-1,2-dihydrophenanthren-4(3H)-one

Birch reduction and reductive methylations of the title compounds have been investigated. 7-Methoxy-3,4-dihydrophenanthren-1(2H)-one (2) yields the cis-3,4,9,10,11,12-hexahydro-derivative (15) while the 7-methoxy-1,2-dihydrophenanthren-4(3H)-one (5) is reduced to the corresponding 1,2,9,10-tetrahydro-derivative (7). The factors influencing the mechanism of the reduction process have been discussed. The reductive methylation products of the ketone (2) are useful substrates in the synthesis of 9-methyl steroids.

Strategies of synthesis of aromatic polyketides using cyclohexa-1,4-and-1,3-dienes in Alder Rickett reactions

Cyclohexa-1, 4-dienes with appropriate substituents, obtained by birch reduction of the substituted benzene, react directly with derivatives of propiolic ester or aldchyde to yield aromatic polyketides. The following compounds have been synthesized; mycophenolic acid, nidulol methyl other, the root growth hormone 3, 5-dihydroxy-2-formyl-4-mythyl-benzoic acid, antibiotic DB 2073, the macrocyclic lactones lasiodiplodin and dihydrozearalenone and the biphenyl derivatives alternario and altenusin. Polyketide anthraquinones can be made from naphthoquinone precursors.

Structure of (4S)-2,4-dimethyl-1,2-dihydropyrazino[2,1-b]quinazoline-3(4H),6-dione

C13HI3N302, orthorhombic, P2~2121, a = 17.443 (5), b = 11.650 (4), c = 5.784 (1)/~, Z = 4, d m = 1.456, d c = 1.429 Mg m -3, F(000) = 512, g(Cu Ka) = 0.843 mm-L The R index is 0.040 for 1358 significant reflections. The structure is stabilized by C-H...O interactions. The N-methylated eis peptide group which forms part of a six-membered ring is non-planar. The torsion angle about the peptide bond is -6.1 (4) ° and the peptide bond length is 1.337 (3) A.

Protein Synthesis in Mycobacterium tuberculosis H37Rv and the Effect of Streptomycin in Streptomycin-Susceptible and -Resistant Strains

An efficient in vitro amino acid-incorporating system from Mycobacterium tuberculosis H37Rv was standardized. Ribonucleic acid (RNA) isolated from phage-infected M. smegmatis cells served as natural messenger RNA and directed the incorporation of 14C-amino acids into protein. The effects of various antitubercular drugs and “known inhibitors” of protein synthesis on amino acid incorporation were studied. Antibiotics like chloramphenicol and tetracycline inhibited mycobacterial protein synthesis, though they failed to prevent the growth of the organism. This failure was shown to be due to the impermeability of mycobacteria to these drugs by use of “membrane-active” agents along with the antibiotics in growth inhibition studies. Several independent streptomycin-resistant mutants of M. tuberculosis H37Rv were isolated. Streptomycin inhibited the incorporation of 14C-amino acids into proteins by whole cells of a streptomycin-susceptible strain by more than 90%, whereas very little or no inhibition was observed in either high-level or low-level streptomycin-resistant strains.

Biochemical effects of 3,5-diethoxycarbonyl-1, 4-dihydrocollidine in mouse liver

3,5-Diethoxycarbonyl-1,4-dihydrocollidine (DDC) is a porphyrinogenic agent and is a powerful inducer of δ-aminolaevulinate synthetase, the first and rate-limiting enzyme of the haem-biosynthetic pathway, in mouse liver. However, DDC strikingly inhibits mitochondrial as well as microsomal haem synthesis by depressing the activity of ferrochelatase in vivo. The drug on repeated administration to female mice has been found to elicit hypertrophic effects in the liver microsomes initially, but the effects observed at later stages denote either hyperplasia or increase in polyploidal cells. The microsomal protein concentration shows a striking decrease with repeated doses of the drug. The rate of microsomal protein synthesis in vivo as well as in vitro shows an increase with two injections of DDC but decreases considerably with repeated administration of the drug. The activities of NADPH-cytochrome creductase and ribonuclease are not affected in the liver microsomes of drug-treated animals when expressed per mg of microsomal protein. DDC has also been found to cause degradation of microsomal haem, which is primarily responsible for the decrease in cytochrome P-450 content. The drug also leads to a decrease in mitochondrial cytochrome c levels due to inhibition of haem synthesis and also due to degradation of mitochondrial haem at later stages. The biochemical effects of the drug are compared and discussed with those reported for allylisopropylacetamide and phenobarbital.

Temporal and spatial patterns of soil water extraction and drought resistance among genotypes of a perennial C-4 grass

The objective of this study was to investigate patterns of soil water extraction and drought resistance among genotypes of bermudagrass (Cynodon spp.) a perennial C-4 grass. Four wild Australian ecotypes (1-1, 25a1, 40-1, and 81-1) and four cultivars (CT2, Grand Prix, Legend, and Wintergreen) were examined in field experiments with rainfall excluded to monitor soil water extraction at 30-190 cm depths. In the study we defined drought resistance as the ability to maintain green canopy cover under drought. The most drought resistant genotypes (40-1 and 25a1) maintained more green cover (55-85% vs 5-10%) during water deficit and extracted more soil water (120-160 mm vs 77-107 mm) than drought sensitive genotypes, especially at depths from 50 to 110 cm, though all genotypes extracted water to 190 cm. The maintenance of green cover and higher soil water extraction were associated with higher stomatal conductance, photosynthetic rate and relative water content. For all genotypes, the pattern of water use as a percentage of total water use was similar across depth and time We propose the observed genetic variation was related to different root characteristics (root length density, hydraulic conductivity, root activity) although shoot sensitivity to drying soil cannot be ruled out.

Crystal and molecular structure of a dimethyl sulphoxide complex with lanthanum nitrate, La(NO3)3.4(CH3)2SO

Abstract is not available.