N-demethylation of cyamemazine via non-classical Polonovski reaction and its conjugation to bovine serum albumin

A modified Polonovski reaction has been employed to obtain the N-demethylated metabolite of the neuroleptic drug cyamemazine. The synthesis involves N-oxide formation, isolation of the corresponding N-oxide, and a FeSO(4)·7H(2)O mediated Polonovski reaction to afford the desired monodesmethyl cyamemazine. In a subsequent step the hapten N-demethylcyamemazine-hemiglutarate was synthesized and its conjugated to bovine serum albumin (BSA).     

Head group-independent interaction of phospholipids with bile salts. A fluorescence and EPR study

Bile salts are essential for phospholipid secretion into the bile. To study the relevance of the structure of phospholipids for their interaction with bile salts, we used spin-labeled or fluorescent phospholipid analogues of different head groups and acyl chain length. Those analogues form micelles in aqueous suspension. Their solubilization by bile salts resulting in the formation of mixed micelles was followed by the decrease of spin-spin interaction of spin-labeled analogues or by the relief of fluorescence self-quenching of (7-nitro-2-1,3-benzooxadiazol (NBD))-labeled analogues. Solubilization of analogue micelles occurred at and above the critical micellar concentration (CMC) of the bile salts. As revealed by stopped-flow technique, solubilization of NBD-analogues was very rapid with half times as low as 0.1 sec above the CMC of taurocholate. Both kinetics and extent of solubilization were independent of the phospholipid head group, but were significantly affected by the fatty acid chain length. Furthermore, using vesicles with varying phospholipid composition and different types of analogues in self-quenching concentrations, we could show that bile salt-mediated vesicle solubilization depended on the fatty acid chain length of phospholipids. In contrast, neither for phospholipids nor for analogues could an influence of the lipid head group on the solubilization process be observed. These findings support a head group-independent mechanism of bile salt-mediated enrichment of specific phospholipids in the bile fluid.     

Effects of iron,copper, and chromate ions on the oxidative degradation of cellulose model compounds

Iron(II) and iron(III) ions promote the degradation of the cellulose model 1,5-anhydrocellobiitol by oxygen or hydrogen peroxide; copper and chromate ions have marked and different effects on the iron catalysis. With starch, iron promotes the hydrogen peroxide-induced reaction and copper and chromate ions further enhance the reaction rate. The tensile strength of paper board is reduced by the action of hydrogen peroxide and iron(II) salts, and mixtures of copper, chromate, and arsenate salts (CCA, a timber preservative) also promote degradation in the presence or absence of iron ions. The oxidation of 1,5-anhydrocellobiitol by oxygen in the presence of iron ions is strongly inhibited by CCA and by cetyltrimethylammonium chloride, and is accelerated by phenols and related compounds.     

负载型纳米铁制备条件对As(V)吸附的影响

以活性炭为载体,制备了负载型纳米铁除砷吸附剂.以除砷效率为目标,优化了制备过程中活性炭的不同粒径、铁盐种类及浓度、反应温度及速度、铁盐浸泡活性炭时间及反应平衡时间等参数.考虑到除砷效率及工程实际的应用,室温时采取活性炭粒径为20～40目、KBH4的滴加速率为lml·min-1、活性炭经铁盐为质量浓度为6.9％的硫酸亚铁浸泡30 min,反应平衡时间为30 min时所制备的吸附剂综合除砷效果最好(98％).     

Further structural studies of zosterine

Traces of either ferrous or ferric salts greatly increase the rate of the stepwise degradation of reducing sugars by alkaline hydrogen peroxide, as measured by formation of formic acid; addition of larger proportions of iron salts causes relatively smaller effects. The results showed that, unless unusually strict precautions are taken to exclude traces of iron, the free-radical cleavage of the hydroperoxide adducts of reducing sugars is far more rapid than the ionic cleavage. The catalytic effect of iron salts is counteracted by addition of magnesium salts. With d-glucose, inhibition of the catalytic effect of iron by magnesium depends on both the magnesium-iron ratio and the concentration at a given ratio. Measurements with various molar proportions of the salts indicated that a magnesium-iron complex, containing six atoms of magnesium to one of iron, is formed. Presumably, removal of iron by formation of this complex inhibits the free-radical degradation of hydroperoxide adducts. In marked contrast to the results obtained with reducing sugars, the degradation of potassium glyoxylate and of glyoxal by alkaline hydrogen peroxide is extremely rapid, and not catalyzed by iron or inhibited by magnesium. The results are in accord with an ionic, rather than a free-radical, cleavage of the hydroperoxide adducts of these compounds. The rapidity of the ionic reaction may be attributed to the ready availability of an electron pair from the adjoining carbon atom.     

On porcine pancreatic colipase: large scale purification and some properties

Two colipases (94–95 and 83–84 residues, respectively) preventing lipase inhibition by bile salts have been purified with a 30% yield from defatted porcine pancreas. In a tributyrin system at pH 6.0, NaTDC¹ was found to inhibit lipase for concentrations (0.20–1.25 mM) below the critical micelle concentration. Ultracentrifugation assays on pure products were consistent with a bile salt-mediated conversion of colipase into another form possessing a higher MW and the ability to give with lipase a bile salt-resistant complex.     

Lipid peroxidation initiated by superoxide-dependent hydroxyl radicals using complexed iron and hydrogen peroxide

Iron salts stimulate lipid peroxidation by decomposing lipid peroxides to produce alkoxyl and peroxyl radicals which initiate further oxidation. In aqueous solution ferrous salts produce OH. radicals, a reactive species able to abstract hydrogen atoms from unsaturated fatty acids, and so can initiate lipid peroxidation. When iron salts are added to lipids, containing variable amounts of lipid peroxide, the former reaction is favoured and OH. radicals contribute little to the observed rate of peroxidation. When iron is complexed with EDTA, however, lipid peroxide decomposition is prevented, but the complex reacts with hydrogen peroxide to form OH. radicals which are seen to initiate lipid peroxidation. Superoxide radicals appear to play an important part in reducing the iron complex.     

Biosynthesis of D-glucaric acid in mammals: a free-radical mechanism?

In the presence of iron salts and hydrogen peroxide, D-glucuronic acid was converted into D-glucaric acid. The reaction was strongly inhibited by free-radical scavengers and is ascribed to the action of the hydroxyl radical. The formation of D-glucarate was dependent upon pH and occurred in the presence of some iron-complexing agents. The first product of oxidation was a lactone that was a strong inhibitor of beta-D-glucuronidase and assumed to be D-glucaro-1,5-lactone. Microsomal preparations in the presence of NADPH also produced D-glucarate from D-glucuronic acid, presumably due to formation of hydrogen peroxide, and the product was an inhibitor of beta-D-glucuronidase. Superoxide did not produce D-glucarate from D-glucuronate. The cytochrome P450 system is more likely than "glucuronolactone dehydrogenase" to be responsible for the production of D-glucaric acid in vivo.     

Challenges and opportunities in the use of iron in water and wastewater treatment

Even though iron salts are widely used in waterand wastewater treatment, many questionssurrounding the use of this element remain.Issues surrounding the impact of mixingconditions on floc structure and strength, theeffect of reduction of ferric iron species onanaerobic sludge properties (includingdewatering) and the possible options for choiceof ligand in the modified photo-Fenton processfor contaminant oxidation are discussed andaspects requiring further attention in theseand other areas involving iron transformationspresented.     

Iron transport in Salmonella typhimurium: mutants blocked in the biosynthesis of enterobactin

A number of mutants of Salmonella typhimurium were isolated which are blocked in the biosynthesis of enterobactin, an iron chelator that is secreted by the wild-type bacteria when they are grown on low iron media. One class of these enb mutants accumulates the enterobactin precursor 2,3-dihydroxybenzoic acid, and another class does not accumulate any detectable catechol precursor. The enb mutants grow very well on a glucose-mineral salts medium. Addition of citrate, itself an iron chelator, to the medium drastically inhibits growth unless the medium is supplemented with enterobactin or iron salts. Citrate inhibits iron uptake from the medium by enb mutants; enterobactin counteracts this inhibition and also, by itself, increases iron uptake. Thus, the apparent function of enterobactin is to promote the absorption of iron from the medium by the bacteria. Transduction experiments showed that the genes for enterobactin biosynthesis are closely linked on the S. typhimurium chromosome. It is suggested that they form an operon which is repressed by the presence of iron. S. typhimurium can utilize the iron chelate ferrichrome. (Deferriferrichrome is a cyclic hexapeptide that is produced by some fungi but not by S. typhimurium.) The enb mutants use ferrichrome as an effective growth factor.     

A Technique for Assessing the Effects of pH and Photodegradation on the Stability of the Iron Chelate of Ethyl N-methyl-4-hydroxy-5-oxo-3-pyrroline-3-carboxylate

Ethyl N-methyl-4-hydroxy-5-oxo-3-pyrroline-3-carboxylate forms a deep red chelate with iron salts. The color intensity is directly related to the iron concentration. The photosta-bility of the red color was determined at pH 1.2 and 5 by spectrophotometric assay at 484 nm at intervals during irradiation by tungsten light at 1020 μW/cm². After 528 hr of continuous irradiation in deionized water, 90.9% of the iron chelate had decomposed. The reaction followed zero order kinetics. Maximal stability was observed at pH 5 at both 10^--² and 10^--² molar concentrations of the iron chelate: no detectable decomposition occurred after 192 hr of continuous irradiation. The iron chelate in biological tissues is stable for 18 months. The staining technique is superior to other histological methods for estimating low concentrations of iron in tissue.     

Hepatic overexpression of murine Abcb11 increases hepatobiliary lipid secretion and reduces hepatic steatosis

Abcb11 encodes for the liver bile salt export pump, which is rate-limiting for hepatobiliary bile salt secretion. We employed transthyretin-Abcb11 and BAC-Abcb11 transgenes to develop mice overexpressing the bile salt export pump in the liver. The mice manifest increases in bile flow and biliary secretion of bile salts, phosphatidylcholine, and cholesterol. Hepatic gene expression of cholesterol 7alpha-hydroxylase and ileal expression of the apical sodium bile salt transporter are markedly reduced, whereas gene expression of targets of the nuclear bile salt receptor FXR (ileal lipid-binding protein, short heterodimer partner (SHP) is increased. Because these changes in gene expression are associated with an increased overall hydrophobicity of the bile salt pool and a 4-fold increase of the FXR ligand taurodeoxycholate, they reflect bile salt-mediated regulation of FXR and SHP target genes. Despite the increased biliary secretion of bile salts, fecal bile salt excretion is unchanged, suggestive of an enhanced enterohepatic cycling of bile salts. Abcb11 transgenic mice fed a lithogenic (high cholesterol/fat/cholic acid) diet display markedly reduced hepatic steatosis compared with wild-type controls. We conclude that mice overexpressing Abcb11 display an increase in biliary bile salt secretion and taurodeoxycholate content, which is associated with FXR/SHP-mediated changes in hepatic and ileal gene expression. Because these mice are resistant to hepatic lipid accumulation, regulation of Abcb11 may be important for the pathogenesis and treatment of steatohepatitis.     

Induced Biosynthesis of Formic Hydrogenlyase in Iron-Deficient Cells of Escherichia coli.

Fukuyama, T. (University of Washington, Seattle), and E. J. Ordal. Induced biosynthesis of formic hydrogenlyase in iron-deficient cells of Escherichia coli. J. Bacteriol. 90:673-680. 1965.-Escherichia coli cells were grown aerobically on a lactate-mineral salts medium from which iron had been removed by extraction with 8-hydroxyquinoline and chloroform. These cells carried out induced biosynthesis of formic hydrogenlyase in a reaction mixture containing glucose, formate, and phosphate without the addition of amino acids, providing adequate amounts of iron salts were present. In the absence of iron, glucose was fermented and acids were produced, but no formic hydrogenlyase developed. When iron-deficient E. coli cells were repeatedly washed, the property of carrying out induced biosynthesis of formic hydrogenlyase with glucose, formate, phosphate, and iron was lost, but was restored on addition of acid-hydrolyzed casein to the reaction mixture. An energy source (provided as glucose) was necessary for enzyme production. Iron-deficient cells were devoid of hydrogenase and formic hydrogenlyase but showed formic dehydrogenase activity when adequate amounts of selenium and molybdenum were present in the growth medium. Hydrogenase was consistently absent in iron-deficient cells but appeared concomitantly with formic hydrogenlyase during induced biosynthesis of the latter in iron-deficient cells of E. coli.     

A postcoupling method for the demonstration of N-acetyl-beta-D-glucosaminidase in unfixed frozen tissue sections.

The localization and activity of the lysosomal enzyme, N-acetyl-beta-glucosaminidase, has been studied in unfixed frozen sections of tissues from normal and hemorrhaged rats with the use of a modified postcoupling technique. Discrete localization of the end product of the reaction was achieved in this method by the incorporation of 20% (w/v) polyvinyl alcohol (molecular weight 14,000) in the incubation medium. Advantages of the present method include the ability to overcome the inhibitory effects on enzyme activity of both tissue fixation and the presence of diazonium salts in the incubation medium. The staining reaction obtained with this technique demonstrates the enzyme activity at specific cytoplasmic sites within cells and has a wider applicability to the comparative study of N-acetyl-beta-glucosaminidase activity in normal and injured tissues.     

Identification of the optochin-resistant Streptococcus pneumoniae strains

So far the prevalent method of the identification of pneumococci in the routine diagnostic practice has included three tests: sensitivity to optoxin, solubility in biliary salts and reaction with omniserum. At present optoxin-resistant pneumococcal strains, as well as those giving dual reaction to solubility in biliary salts, occur sufficiently often thatconsiderably complicates the identification of this infective agent. We have summarized experience in the isolation of S. pneumoniae strains, resistant to optoxin and not soluble in biliary salts; in addition, the prospects of introducing the complex approach to the identification of a given culture with the use of molecular diagnostic methods into daily practice are evaluated.     

Preparation of metal ion buffers for biological experimentation: a methods approach with emphasis on iron and zinc

Transition metal ions are a challenge to study in physiology because of problems associated with solubility, oxidation, binding, and attaining appropriate free activities in solution. This review discusses these problems and potential ways of accommodating them. Special attention is given to iron and zinc ions, but many of the concepts can be applied for studying other transition metals. Selection of reagents appropriate for metal work (including water, salts, noncomplexing pH buffers) is briefly discussed. Calculation of the solubility product (K(sp)) for common iron and zinc precipitates is covered, as well as techniques used to solubilize Fe(3+) with organic chelates. Factors that affect Fe(2+) oxidation are mentioned, and the use of ascorbate as a reducing agent is considered. Measurement of the rate of Fe(2+) oxidation (or Fe(3+) reduction) with the Fe(2+) chromophores ferrozine and BPS is also discussed. Generation of a free metal ion activity through use of metal buffers (chelators) is discussed. Theoretical problems associated with this technique are explored, and selected shareware metal ion buffer calculators are described. Finally, techniques for measuring and minimizing nonspecific binding of iron and zinc ions to biological membranes are considered.     

The conversion of procyanidins and prodelphinidins to cyanidin and delphinidin

The hydrolysis of proanthocyanidins to anthocyanidins in n-BuOH-HCl (95:5) has been shown to be an autoxidation, the yield of anthocyanidin being critically dependent on trace metal-ion impurities. Reproducible yields of anthocyanidin may be achieved if iron (III) salts are added to the reaction medium, and a standard method of analysis of proanthocyanidins based on use of an n-BuOH-HCl-Fe^III mixture is given. The ratio of absorbance maxima of the cyanidin (550 nm) produced to that near 280 nm for the original procyanidin polymer solution was ～ 3.5.     

Synthesis of Polyfused Heteroaromatics by Palladium-Catalyzed Cross-Coupling Reaction

The palladium-catalyzed coupling of unsaturated halides or triflates with organostannanes (the Stille reaction) or with organo-boronic acids (the Suzuki reaction) has envolved as a powerful means of carbon-carbon bond formation. As an extention of our work on the synthesis and reactivity of positively charged bridge-head nitrogen containing fused azinium salts, we have been studying the formation of polyfused heteroaromatics with angular anellation pattern. The reaction of such positively charged salts with nucleophiles has proven to be a suitable tool for the preparation of heteroaryl dienes, which have been shown to be excellent intermediates for several ring closure reaction. A selection of results will be presented, including applications to natural product synthesis.     

Inhibition of the iron-catalysed formation of hydroxyl radicals from superoxide and of lipid peroxidation by desferrioxamine.

The peroxidation of membrane phospholipids induced in vitro by ascorbic acid or by dialuric acid (hydroxybarbituric acid) does not occur in the absence of traces of metal ions. Peroxidation induced by adding iron salts to phospholipids can either be promoted or inhibited by the chelators EDTA, diethylenetriaminepenta-acetic acid and bathophenanthrolinesulphonate, depending on the ratio [chelator]/[iron salt]. The iron chelator desferrioxamine inhibits peroxidation at all concentrations tested, and it also inhibits the iron-catalysed formation of hydroxyl radicals (OH.) from superoxide (O2-.). Since desferrioxamine is approved for clinical use, it might prove a valuable tool in the treatment of inflammation, poisoning by autoxidizable molecules and radiation damage.