Effect of aluminum ion on Fe(2+)-induced lipid peroxidation in phospholipid liposomes under acidic conditions

The effects of Al3+ on Fe(2+)-induced lipid peroxidation in phospholipid liposomes consisting of phosphatidylcholine (PC) and phosphatidylserine (PS) were examined under acidic conditions. The stimulatory effect of Al3+ on Fe(2+)-induced lipid peroxidation in the liposomes showed a biphasic response against pH variation, and the maximum stimulation was observed around pH 6.0. In addition, it was found that the stimulatory effect of Al3+ on the lipid peroxidation was dependent on the proportion of PS in the liposomes. On the other hand, the lipid peroxidation in PC liposomes was not stimulated by the addition of Al3+. From these findings, it is suggested that the Al3+ effect on Fe(2+)-induced lipid peroxidation under acidic conditions is largely dependent on the phospholipid composition. Trivalent cations such as Tb3+ and Ga3+ also stimulated Fe(2+)-induced lipid peroxidation in PC/PS liposomes under acidic conditions, but divalent cations (Zn2+ and Mn2+) showed no stimulatory effect. The extents of Fe2+ disappearance and Fe3+ formation during the reaction were enhanced by the addition of Al3+ or Ga2+, but Tb3+ had no effect on Fe2+ disappearance. The results with 1,6-diphenyl-1,3,5-hexatriene (DPH) showed that the fluorescence anisotropy of DPH-labeled PC/PS liposomes under acidic conditions was increased by the addition of Al3+. Furthermore, there is a relation between the extents of the fluorescence anisotropy of the complex and TBARS production. In contrast, the fluorescence anisotropy of DPH molecules embedded in PC liposomes was not changed by the addition of Al3+. Based on these results, a possible mechanism of the stimulatory effect of Al3+ on Fe(2+)-induced lipid peroxidation under acidic conditions is discussed.     

Effect of aminoguanidine on erythrocyte lipid peroxidation and activities of antioxidant enzymes in experimental diabetes

We report on six unrelated children, three boys and three girls, with a metaphyseal dysplasia of early onset and spontaneous regressing evolution. During the first months of life the children present with enlargement of costochondral junctions and knobby wrists. On radiographs the metaphyseal changes of the knees are specific with fine irregularities. The femoral necks are blurred but not hypoplastic. The stature is not affected and there are no metabolic abnormalities. The radiographic findings regress during growth and the abnormalities disappear after the age of ten years. These metaphyseal changes and their mode of inheritance are different from previous cases described as anadysplasia. We propose therefore to delineate this syndrome as a new type of regressive metaphyseal dysplasia and to name it anadysplasia type II.     

Susceptibility to in vitro lipid peroxidation of low density lipoproteins and erythrocyte membranes from liver cirrhotic patients

All retinoic acid receptors (RAR alpha, beta, gamma) have two isoforms, whose function is unknown. We now show that at least for RAR gamma, the isoforms are differentially distributed in the embryo. RAR gamma 1 and RAR gamma 2 are detected in the head region, whereas RAR gamma 2 is the sole isoform expressed in the tail region. Specifically, it is expressed in the chordoneural hinge, a region of the tailbud that has organizing properties. Treatment with high doses of retinoic acid (RA) reduces expression in this region. The results are discussed in terms of the known teratogenic effects of RA in the tail region.     

Inhibition of 2,2'-azobis(2,4-dimethylvaleronitrile)-induced lipid peroxidation by sesaminols

We found that sesaminols, a mixture of sesaminol and its stereoisomers, are potent inhibitors of the oxidation of low-density lipoprotein induced by 2,2'-azobis(2,4-dimethylvaleronitrile). Although sesaminols strongly inhibit lipid peroxidation related to their ability to scavenge free radicals, their antioxidant effects have not been investigated. To confirm the involvement of the phenolic moiety in the sesaminol structure in antioxidant activity, sesaminols were reacted with 2,2'-azobis(2,4-dimethylvaleronitrile). The reaction products were isolated by high-performance liquid chromatography and found to have a 1-cyano-1,3-dimethyl-butyl-peroxyl group in their structures. These chemical structures suggest that the sesaminols reacted with the alkylperoxyl radicals to form four major reaction products that are stereoisomers of each other, although the stereochemistry of each isomer has not yet been confirmed. Further instrumental analyses of the reaction products may increase our understanding of the antioxidant activity of sesaminols.     

Flip-flop of doxorubicin across erythrocyte and lipid membranes

Doxorubicin, an anticancer drug, is extruded from multidrug resistant (MDR) cells and from the brain by P-glycoprotein located in the plasma membrane and the blood-brain barrier, respectively. MDR-type drugs are hydrophobic and, as such, enter cells by diffusion through the membrane without the requirement for a specific transporter. The apparent contradiction between the presumably free influx of MDR-type drugs into MDR cells and the efficient removal of the drugs by P-glycoprotein, an enzyme with a limited ATPase activity, prompted us to examine the mechanism of passive transport within the membrane. The kinetics of doxorubicin transport demonstrated the presence of two similar sized drug pools located in the two leaflets of the membrane. The transbilayer movement of doxorubicin occurred by a flip-flop mechanism of the drug between the two membrane leaflets. At 37 degrees, the flip-flop exhibited a half-life of 0.7 min, in both erythrocyte membranes and cholesterol-containing lipid membranes. The flip-flop was inhibited by cholesterol and accelerated by high temperatures and the fluidizer benzyl alcohol. The rate of doxorubicin flux across membranes is determined by both the massive binding to the membranes and the slow flip-flop across the membrane. The long residence-time of the drug in the inner leaflet of the plasma membrane allows P-glycoprotein a better opportunity to remove it from the cell.     

Modulation of bilayer fluidity by lipid peroxidation of human placental syncytiotrophoblast membranes during embryogenesis

BACKGROUND: Hand eczema (HE) is a chronic multifactorial dermatosis with the presence of endogenous and exogenous factors in its pathogenesis. The etiologic diagnosis of hand eczema is often difficult. OBJECTIVES: The objectives of this study were (1) to detect clinical history and clinical examination data capable of differentiating HE types; (2) to determine the importance of patch tests for the etiologic diagnosis of HE; and (3) on the basis of the definitive diagnosis of HE type with the aid of patch tests, to obtain relevant data for appropriate patient guidance for the control of HE. METHODS: A total of 250 patients with HE were studied over a period of 3 years (1993 to 1995). All patients were submitted to the battery of patch tests. RESULTS AND CONCLUSIONS: The results obtained led to the following conclusions: (1) Women are more predisposed to HE. (2) Work under moist conditions favors HE. (3) With respect to the regional location of HE, any region may be involved in any type of HE; however, involvement of the dorsal region is more common in allergic contact dermatitis (ACD), followed by contact dermatitis owing to primary irritation (ICD) and atopic dermatitis (AD). Location of HE on the dorsal surface of the fingers was mainly observed in ACD, followed by ICD and AD. (4) Patch tests should be part of the investigative routine of HE etiology. (5) The presence of allergy to metals in the clinical history of the patient is a relevant feature, because patch tests confirmed sensitization to nickel in 89% of cases. (6) Rubber components have high sensitization frequency in patients with HE. (7) When the patient reports worsening of HE after the use of rubber gloves, this indicates a probable sensitization to rubber components, mainly in patients with AD.     

Ornithine decarboxylase inactivation by putrescine: involvement of lipid peroxidation

Effect of polyamines on 12-O-tetradecanoyl phorbol-13-acetate (TPA)-induced reduction of lipid peroxidation was studied. Putrescine protected this lowering of lipid peroxidation in a concentration-dependent manner, but spermidine or spermine could not do so. Putrescine also inhibited the TPA-induced ornithine decarboxylase (ODC) activity and lowered the free sulfhydryl content of TPA exposed mouse skin. These observations indicate that putrescine inactivates ODC probably by lowering SH groups through lipid peroxidation.     

Effects of La3+ on lipid fluidity and structural transitions in human erythrocyte membranes

Laparoscopic pyeloplasty is one of several minimally invasive treatment options for UPJ obstruction. In fact, several endoscopically and fluoroscopically controlled methods of incising the obstructed UPJ are now available that are significantly less invasive and less morbid in comparison with open pyeloplasty. However, the long-term success rates of these incisional techniques are less than the rates reported for open pyeloplasty. Several causes of obstruction may be present in the primarily obstructed UPJ, including kinking or compression related to crossing vessels or intrinsic narrowing at the UPJ. One potential reason for the inferior success rates of incisional methods in comparison with open pyeloplasty is that the former techniques address the intrinsically narrowed UPJ but may not address extrinsic problems such as kinking of the ureter associated with fibrotic bands or compression from crossing vessels. Laparoscopic pyeloplasty addresses all potential causes of obstruction. Any fibrotic bands kinking the ureter are divided, and the ureter is spatulated through the level of the UPJ prior to completion of the anastomosis. If a crossing vessel is encountered, a dismembered pyeloplasty is performed, the ureter and renal pelvis are transposed to the opposite side of the vessels, and the anastomosis is completed. An additional disadvantage of incisional techniques is the significant risk of hemorrhage following incision of the UPJ, with as many as 3% to 11% of patients requiring blood transfusion. Hemorrhage may occur owing to an errant anterior incision, the presence of a crossing vessel, incision into the renal parenchyma adjacent to the UPJ, or as the result of bleeding from the percutaneous access site. In contrast, mean estimated blood loss in the authors' series of 57 laparoscopic pyeloplasties was 139 mL, and none of the patients required blood transfusion. Although it is more morbid in comparison with retrograde or fluoroscopically controlled endopyelotomy, laparoscopic pyeloplasty seems at least comparable to antegrade percutaneous endopyelotomy in terms of the length of hospitalization and patient convalescence. Laparoscopic pyeloplasty, however, offers a higher success rate than with incisional techniques, not only from a radiographic standpoint but from a subjective standpoint as determined by the results of the analogue pain and activity questionnaire. The major disadvantage of laparoscopic pyeloplasty is the need for proficiency in laparoscopic techniques and for a longer operative time. As a result, the literature on laparoscopic pyeloplasty consists primarily of small series. Janetschek and co-workers reported on a series of 17 patients who underwent laparoscopic pyeloplasty, including 14 via a transperitoneal approach and 3 via a retroperitoneal approach. Procedures performed included ureterolysis alone, dismembered pyeloplasty, and nondismembered (Fenger) pyeloplasty. "Fenger-plasty" is similar to Y-V pyeloplasty and is performed by incising the UPJ longitudinally and closing the incision transversely in a Heineke-Mikulicz fashion. Janetschek and colleagues reported a 100% success in the eight patients who underwent dismembered pyeloplasty but believed that this technique was too cumbersome and should be reserved for patients with long stenoses, dorsally crossing vessels, or large renal pelvis. Because two of the four patients undergoing ureterolysis alone failed treatment, Janetschek and colleagues have abandoned this technique. They now prefer the Fenger-plasty technique, even in the setting of ventrally crossing vessels, because the technique can be performed quickly with one to three sutures, and the anastomosis can be sealed with fibrin glue and a flap of Gerota's fascia. Their experience with this technique, however, remains relatively limited. Technologic advances such as the Endostitch device have facilitated reconstructive laparoscopic procedures such as pyeloplasty. (ABSTRACT TRUNCATED)     

Inhibition of lipid peroxidation in the erythrocyte membrane by quaternary morpholinium salts with antioxidant function

Camillo Golgi (1843-1926) was born at Corteno, near Brescia, in northern Italy. After graduating in Medicine at the ancient University of Pavia, the former seat of great scientists and naturalists, Golgi continued a long-standing Italian tradition by studying the histology of the nervous system. While working as a modest physician at Abbiategrasso, a small town near Pavia, he developed a silver-osmium technique, the "reazione nera" (black reaction), for which he was awarded the Nobel Prize in 1906. In the late 1890's, 25 years after the publication of his black reaction and while Professor of General Pathology in Pavia, Golgi noticed a fine internal network in only partially silver-osmium-blackened Purkinje cells. Following confirmation by his assistant Emilio Veratti, Golgi published the discovery, called the "apparato reticolare interno", in the Bollettino della Società medico-chirurgica di Pavia in 1898, which is now considered the birthday of the "Golgi apparatus". The discovery of the Golgi apparatus can be added to the long list of accidental discoveries. The man after whom it is named was not a cytologist engaged in studying the inner structure of the cell, but a pathologist searching to prove a neuroanatomical theory.     

Luminescence properties of Tm^3＋/Yb^3＋, Er^3＋/Yb^3＋ and Ho^3＋/Yb^3＋ activated calcium tungstate

CaWO4 phosphor activated by the Tm3+/Yb3+,Er3+/Yb3+ and Ho3+/Yb3+ ions were synthesized by a traditional high-temperature solid-state method.The crystal structures and morphologies of the products were characterized by X-ray powders diffraction method(XRD) ,infrared spectra(FT-IR) and scanning electron microscopy(SEM) .The samples were found to show up-conversion luminescence properties.CaWO4 doped with Tm3+/Yb3+ showed blue luminescence characteristic of Tm(III) ion in the range of 460-485 nm,corresponding to the 1G4→3H6 electronic transition.CaWO4 doped with Er3+/Yb3+ showed strong green luminescence at 510-565 nm(2H11/2,4S3/2→4I15/2) and weak red luminescence at 640-685 nm(4F9/2→4I15/2) of Er(III) ion.CaWO4 doped with Ho3+/Yb3+ phosphor emitted green luminescence at 525-560 nm(5S2,5F4→5I8) and red luminescence at 630-670 nm(5F5→5I8) and at 730-770 nm(5S2,5F4→5I7) ,which is the characteristic of Ho(III) ion.     

Enhanced lipid peroxidation in patients during coronary artery bypass grafting

Lipid peroxidation products were measured at various time intervals in 20 patients with coronary artery disease, who underwent coronary artery bypass graft (CABG) surgery. Post-operative blood lipid peroxides were found to be significantly higher (p < 0.001) than the preoperative value. Lipid peroxides raised to a peak value of 46.42 +/- 12.86 n mol/g Alb at 5 min of reperfusion when compared to the basal value and afterwards the level declined to 41.02 +/- 7.09 at 2 hrs and remained in that level even at 24 hrs of reperfusion. This increase implies an enhancement in free radical mediated oxidation of membrane lipids during bypass surgery and thus provides evidence for free radical generation during myocardial reperfusion.     

Ganglioside GM1 protects cAMP 3'5':phosphodiesterase from inactivation caused by lipid peroxidation in brain synaptosomes of rats

The preincubation of synaptosomes with nanomolar concentrations of ganglioside GM1 was shown to protect Ca(2+)-dependent and Ca(2+)-independent cyclic nucleotide phosphodiesterase from inactivation caused by lipid peroxidation (LPO) induction. Thus, Ca(2+)-dependent phosphodiesterase activity decreased to approximately 34% of the initial value following 30 min of LPO induction, but it constituted more than 60% of the control activity if synaptosomes were preincubated with 10(-8)M GM1, the difference being statistically significant. 10(-6)M alpha-tocopherol had a similar effect. As far as the lipid matrix is concerned, gangliosides were found to prevent to a great extent malonic dialdehyde (MDA) accumulation and to protect polyenoic fatty acids from oxidative destruction. The ability of gangliosides to protect phosphodiesterase from inactivation caused by LPO induction appears to be owing not only to the inhibition of the accumulation of LPO products, but to the direct activation of the enzyme as well, 10(-7) M of ganglioside GM1 having the maximal activating effect. In contrast to alpha-tocopherol and other antioxidants reacting directly with free radicals, the inhibitory effect of gangliosides appears to be mediated by signal transduction systems.     

Ca(2+)-induced conformational transitions of phosphorylated peptides

CD spectroscopic studies on protected peptides containing lysine and serine, or phosphoserine, and on serine-containing fragments of the neurofilament protein midsized subunit, both in the unphosphorylated and phosphorylated form, are reported. The introduction of the phosphoryl group was not found to have a significant spectral effect in aqueous solution. In trifluoroethanol (TFE), spectral shifts toward unordered (type U) spectra or the appearance of distorted spectra likely reflect the adoption of aperiodic polypeptide conformations due to salt bridge(s) between negatively charged phosphoserine and positive lysine side-chain groups. A turn-stabilizing effect of phosphorylation was also observed. CD-monitored titration experiments in TFE revealed a high conformational sensitivity of phosphopeptides toward Ca2+ ions. The appearance of the unordered spectra or spectral shifts were the sign of a bulk disordering effect of Ca2+ ions. Spectra with specific spectroscopic features reflect the formation of Ca2+ complexes and the adoption of ordered unique backbone conformations. When ordered structures were obtained on addition of Ca2+ ions, the observed CD curves showed a resemblance to the spectrum of beta-pleated sheets. This may originate from chain extension and the formation of beta-pleated sheet segments fixed by Ca2+ bridges between PO3H-1 groups of adjacent peptide chains. The data clearly show that the effect of the Ca2+ ions is highly specific: the sequence, chain length, presence and distribution of charged side-chain groups, degree and site of phosphorylation, and environmental factors appear to be determining in the process of chain extension or beta-sheet formation.     

Energy transfer from Ce~(3+) to Tb~(3+) and Eu~(3+) in zinc phosphate glasses

Ce3+,Eu3+ and Tb3+ singly doped and Ce3+/Eu3+ and Ce3+/Tb3+ co-doped zinc phosphate glasses were prepared by sintering P2O5,ZnO,Ce2(C2O4)3·10H2O and Eu2O3/Tb4O7 mixtures at 1200 °C in the air for 2 h and then annealing at 450 °C for 10 h.The obtained glasses were homogeneous and transparent.The glasses without Ce3+ were colorless and those with Ce3+ showed slightly yellow.The singly doped glasses showed strong emissions and excitations from doped trivalent rare earth ions.Strong energy transfer from Ce3+ to Tb3+ was observed for Ce3+/Tb3+ coped samples.There were also some very weak evidences for the energy transfer from Ce3+ to Eu3+.     

Ethane: a marker of lipid peroxidation during cardiopulmonary bypass in humans

The goals of this study were to (1) determine the utility of quantification of ethane as a marker of ischemia-reperfusion during human cardiopulmonary bypass (CPB); and (2) determine, using an animal model for this surgical procedure, whether the mode of surgical approach produced increases the quantity of exhaled ethane. Human CPB was initiated following standard anesthetic and monitoring regimens. Samples of gas were collected at baseline and at multiple defined time points throughout the studies. Ethane was determined using cryogenic concentration and gas chromatography. Sternotomy increased exhaled ethane compared to baseline (p < .007; 5.8 +/- 1.7 vs. 3.0 +/- 0.7 nmol/m2 x min); ethane returned to baseline levels prior to the initiation of CPB. Aortic unclamping produced ethane elevation (p < .05; 2.3 +/- 0.8 vs. 1.5 +/- 0.4 nmol/m2 x min) with the levels being related to a lower cardiac index and a higher systemic vascular resistance post aortic unclamping. Termination of CPB significantly increased ethane levels compared to baseline (p < .002; 4.8 +/- 1.7 vs. 3.0 +/- 0.7 nmol/m2 x min). Independent variables that correlated with increased ethane measurements included a higher arterial blood pH on bypass and the change in hemoglobin pre- and post-CPB. Electrocautery, but not scalpel, incision of the porcine abdominal wall increased ethane levels significantly (p < .02). These results indicate that exhaled ethane may be a valuable marker of lipid peroxidation during and following CPB.     

Anti-oxidant enzymes, gamma-glutamyl transpeptidase and lipid peroxidation in kidney of rats exposed to cigarette smoke

Glutathione reductase (GR), glutathione peroxidase (GSH Px) and catalase (Cat) were determined in the kidneys of rats exposed to cigarette smoke for 3 months. Activity of the brush-border enzyme gamma-glutamyl transpeptidase (GGT), glutathione (GSH) and lipid peroxide levels (LPX) were also estimated in both, kidney homogenates and urine. Activities of GR, Cat, GGT and the levels of GSH were decreased in the kidney. However, the activities of GSH Px and LPX levels were increased. Urinary excretion of GGT, GSH and LPX were also higher. Fall in the activity of GR and rise in the activity of GSH Px, may perturb the reduced glutathione/oxidised glutathione ratio, which in turn could lead to increased LPX seen in chronic cigarette smoke exposure.     

Protoporphyrin-induced photodynamic effects on band 3 protein of human erythrocyte membranes

In previous studies it has been shown that protoporphyrin-induced photodynamic effects on red blood cells are caused by photooxidation of amino acid residues in membrane proteins and by the subsequent covalent cross-linking of these proteins. Band 3, the anion transport protein of the red blood cell membrane, has a relatively low sensitivity to photodynamic cross-linking. This cannot be attributed to sterical factors inherent in the specific localization of band 3 in the membrane structure. Solubilized band 3, for instance, showed a similar low sensitivity to cross-linking. By extracellular chymotrypsin cleavage of band 3 into fragments of 60,000 and 35,000 daltons it could be shown that both fragments were about equally sensitive to photodynamic cross-linking. The 17,000 dalton transmembrane segment, on the other hand, was completely insensitive. Inhibition of band 3-mediated sulfate transport proceeded much faster than band 3 interpeptide cross-linking, presumably indicating that the inhibition of transport is caused by photooxidation of essential amino acid residues or intrapeptide cross-linking. A close parallel was observed between photodynamic inhibition of anion transport and decreased binding of 4,4'-diisothiocyanodihydrostilbene-2,2'-disulfonate (H2DIDS), suggesting that a photooxidation in the immediate vicinity of the H2DIDS binding site may be responsible for transport inhibition.