Mouse liver selenium-binding protein decreased in abundance by peroxisome proliferators

Several studies with two-dimensional gel electrophoresis (2-DE) have shown that the abundance of numerous mouse liver proteins is altered in response to treatment with chemicals known to cause peroxisome proliferation. The peptide masses from tryptic digests of two liver proteins showing dramatic decreases in abundance in response to numerous peroxisome proliferators were used to search sequence databases. The selenium-binding protein 2 (SBP2 formerly 56 kDa acetaminophen-binding protein, AP 56) and selenium-binding protein 1 (SBP1 formerly 56 kDa selenium-binding protein, SP 56) in mouse liver, proteins with a high degree of sequence similarity, were the highest ranked identities obtained. Identity with SBP2 was subsequently confirmed by immunodetection with specific antiserum. Treatment of mice with 0.025% ciprofibrate resulted in the more basic of this pair of proteins being decreased to 30% of control abundance while the acidic protein was decreased to 7% of the control amount. Dexamethasone treatment, in contrast, caused increases of 80% and 20% in the abundance of the acidic and basic forms, respectively. Administration of dexamethasone to mice in combination with ciprofibrate produced expression of the acidic SBP2 at 23% of the control level and the basic SBP2 at 36%, a slightly moderated reduction compared with the decrease that occurred with ciprofibrate alone. These data suggest that peroxisome proliferators such as ciprofibrate cause a decrease in the abundance of the SBP2, which leads to increased cell proliferation, even in the presence of an inhibitor such as dexamethasone. Such a decrease in SBP, thought to serve as cell growth regulation factors, could be central to the nongenotoxic carcinogenicity of the peroxisome proliferators observed in rodents.     

Role of thiol-disulfide exchange in insulin binding to its receptor.

The effects of reduction by DTT, oxidation by DTNB and treatment with NEM on the thiol contents and insulin binding to its receptor in mice liver membranes were studied. Reduction with DTT leads to a parallel increase in the thiol content and the specific binding of insulin to the membrane. Scatchard analysis of the results shows little change in the number of binding sites but a twofold increase of the binding constant. Washing the membrane with bound insulin by a DTT containing buffer results in a more marked increase in the release of bound insulin than washing with buffer alone, suggesting that part of the insulin is bound to its receptor by covalent disulfide linkages through a thiol-disulfide exchange reaction and reduction with DTT leads to a marked increase in this "disulfide-linked" insulin. Treatment with DTNB or NEM of the DTT-reduced membrane seems to reverse the effect of DTT reduction, although the reaction of the untreated membrane with DTNB or NEM had little or no effect on the specific binding of insulin. It is suggested that initially, part of the thiols responsible for the exchange reaction may not be available for reaction with DTNB and reduction with DTT generates further thiols leading to increased specific binding in general and increased insulin binding to the receptor through covalent disulfide linkages in particular.     

Investigation of Metal State in Metal-containing Zeolite Catalysts by DTA and ESR Methods

Thermal stability and its influence on the catalytic activity in CO oxidation of Cu, Pd and Pd-Cu zeolite systems were investigated. The increasing of catalytic activity in the first cycle of reaction is connected with the thermal decomposition of complexions and consequently with the changing of metal state in catalyst in the case of Cu/ZSM-5catalyst. This activity does not relate to initial zeolite with complex ions, but to the metal ions with the decreasing ligands number in the coordination sphere of metal ion. According to the EPR spectrum the copper ions form clusters in zeolite channels due to the spin changed interaction. It was established ESR method that 1.8% Cu/ZSM-5 catalyst in a reduced form has copper (I and II) ions by. The Pd/ZSM-5 catalysts with different metal content have high catalytic activity below the temperature decomposition in contrary to Cu-containing zeolites. On the one hand, it may be connected with the partial reduction of Pd ions during CO oxidation and, on the other hand, with the ability of Pd ions to form the respective label complexes with reagents as additional ligands. The same character of relation between thermal stability and catalytic activity for Pd-Cu/ZSM-5 catalyst was observed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ultrafast study of p-biphenylyldiazomethane and p-biphenylylcarbene

p-Biphenylyldiazomethane was excited by femtosecond pulses of UV light in acetonitrile, in cyclohexane, and in methanol. Ultrafast photolysis produces a singlet excited state of p-biphenylyldiazomethane with lambdamax = 490 nm, and lifetimes of less than 300 fs in acetonitrile, in cyclohexane, and in methanol. The decay of the excited state is accompanied by the growth of transient absorption with lambdamax = 360 nm. The carrier of this transient absorption is attributed to singlet p-biphenylylcarbene, a result that is consistent with the predictions of TD-DFT calculations. The singlet carbene lifetimes are 200 and 77 ps in acetonitrile and cyclohexane, respectively, and are controlled by intersystem crossing to the lower energy triplet state. The transient absorption does not decay to baseline in acetonitrile, because of the formation of nitrile ylide. The equilibrium mixture of singlet and triplet p-biphenylylcarbene reacts with acetonitrile to form a nitrile ylide (lambdamax = 370 nm), and with cyclohexane by C-H insertion 1-20 ns after the laser pulse. The singlet carbene lifetime is only 7.9 ps in methanol, owing to a rapid reaction with the solvent. Reaction with the solvent gives rise, in part, to a p-biphenylylbenzyl cation (lambdamax = 450 nm, tau = 6.3 ps) in methanol.     

Effect of pH on H2O2 production in the radiolysis of water

The yields of hydrogen peroxide have been measured in the radiolysis of aqueous solutions of acrylamide, bromide, nitrate, and air in the pH range of 1-13. Hydrogen peroxide is the main stable oxidizing species formed in the radiolysis of water, and its long-term yield is found to be very sensitive to the system used in the measurements. Experiments with γ-irradiation combined with model calculations show that the primary yields of hydrogen peroxide are nearly independent of pH in the range of 2-12. Slightly higher primary yields are suggested at very low pH in particular when O(2) is present, while the yields seem to decrease at very high pH. Irradiations were performed with 5 MeV H ions, 5 MeV He ions, and 10 MeV C ions to evaluate the intratrack and homogeneous kinetic contributions to H(2)O(2) formation with different ions. Many of the trends in hydrogen peroxide yields with pH observed with γ-irradiations are observed with irradiation by the heavy ions. The lower yields of radicals in the homogeneous phase with the heavier ions tend to minimize the effects of radicals on the hydrogen peroxide yields at long times.     

偶联剂对丙烯酸酯改性聚氨酯聚合物接枝率和乳液性能的影响

合成了含双羟基的甲基丙烯酸甘油酯(GM)并将其作为偶联剂用于聚丙烯酸酯(PAC)对水基聚氨酯(PU)的改性.采用核磁共振、红外光谱和气相色谱等对GM进行了表征.分别以该双羟基GM和单羟基的丙烯酸羟乙酯(HEA)与异氰酸酯基(NCO)封端的PU预聚体进行反应以在PU分子链上引入双键,然后再与丙烯酸酯类单体通过自由基聚合制...     

Preparation of vinylogous 2-sulfonylindolines by the palladium-catalyzed heteroannulation of o-iodoanilines with dienyl sulfones and their further transformation to indoles and carbazoles.

The palladium-catalyzed heteroannulation of o-iodoanilines with dienyl sulfones provides a convenient route to vinylogous 2-sulfonylindolines 3. The reaction proceeds in DMF/water in the presence of potassium carbonate and catalytic palladium(II) acetate and is compatible with both electron-donating and -withdrawing substituents in the para position of the aniline, and with an alkyl substituent at C-2 of the dienyl sulfone. The indolines underwent oxidation with DDQ to afford the corresponding indoles 4. The latter were then employed as dienes in Diels-Alder reactions with dimethyl acetylenedicarboxylate (DMAD), methyl propiolate, or methyl acrylate. In the case of the latter two dienophiles, the cycloadditions were highly regioselective, affording the corresponding 1,3-products (with respect to the relative positions of the sulfone and ester groups), exclusively. The cycloadducts from acetylenic dienophiles were converted to the corresponding carbazoles by elimination of the sulfone moiety with DBU, and that from methyl acrylate was subjected to reductive desulfonylation and oxidation to the corresponding carbazole with DDQ. The method thus provides access to carbazoles with various substituents at the 3-, 4-, and 6-positions.     

Bone marrow scintigraphy with 111In-chloride--a clinical value for the hematological diseases

Bone marrow scintigraphy with indium chloride (111In) was performed in fifty-one patients with the hematological diseases. The results of the investigation were that 1. in all patients, as well as in patients with aplastic anemia, no correlation was there between the degree of the indium chloride accumulation and peripheral blood counts, 2. in patients with aplastic anemia and pure red cell aplasia (PRCA) a tendency to reduction in uptake of indium chloride in bone marrow, 3. in patients with these two good correlation between the degree of indium chloride accumulation and histology of the erythroid bone marrow, but in patients with chronic myelocytic leukemia (CML) and atypical leukemia no correlation between the two, so it seemed unlikely that indium chloride should reflect the effective production of erythrocytes, 4. four patients with leukemia were studied with indium chloride bone marrow imaging two times to evaluate their responses to chemotherapy, and peripheral expansion was no change or reduced in two patients with acute myelocytic leukemia (AML) and one patient with acute lymphocytic leukemia (ALL) who obtained complete remission, but on the other hand, it enlarged in one patient with acute myelocytic leukemia who obtained partial remission, and 5. in two patients with chronic myelocytic leukemia it enlarged up to the ankle joints, which was considerably specific.     

ROLE OF THIOL-DISULFIDE EXCHANGE IN INSULIN BINDING TO ITS RECEPTOR

The effects of reduction by DTT, oxidation by DTNB and treatment with NEM on the thiol contents and insulin binding to its receptor in mice liver membranes were studied. Reduction with DTT leads to a parallel increase in the thiol content and the speciflc binding of insulin to the membrane. Scatchard analysis of the results shows little change in the number of binding sites but a twofold increase of the binding constant. Washing the membrane with bound insulin by a DTT containing buffer results in a more marked increase in the release of bound insulin than washing with buffer alone, suggesting that part of the insulin is bound to its receptor by covalent disulfide linkages through a thIol-disulfide exchange reaction and reduction with DTT leads to a marked increase in this "disulfide-linked" insulin. Treatment with DTNB or NEM of the DTT-reduced membrane seems to reverse the effect of DTT reduction, although the reaction of the untreated membrane with DTNB or NEM had little or no effect on the specific     

Heavy ion radiolysis of liquid pyridine

The radiation chemical yields of the main products produced in liquid pyridine radiolysis (molecular hydrogen and dipyridyl) have been examined as a function of particle linear energy transfer (LET) with protons, helium ions, and carbon ions of a few to 30 MeV and compared to gamma-radiolysis published in a previous work (J. Phys. Chem. A 2005, 109, 461). Anthracene and biphenyl scavenging techniques have been used to clarify the role of the triplet excited state. An increase in triplet scavenger concentration leads to a decrease in pyridine triplet excited state with a concurrent decrease in dipyridyl, but formation of the latter does not primarily involve pyridyl radicals expected to be produced in the decomposition of the triplet excited state. A decrease in the yield of dipyridyl and an increase in molecular hydrogen are observed with increasing track average LET. The dipyridyl yield with 10 MeV carbon ions is 0.20 molecules/100 eV, which is only 16% of that of observed with gamma-rays. The low yield of dipyridyl with carbon ions is attributed to intratrack triplet-triplet (T-T) annihilation processes due to the increase in local triplet excited-state concentrations with increasing LET. An increasing yield of molecular hydrogen with increasing LET is probably due to an increase in the formation and subsequent decay of singlet excited states produced by the T-T annihilation. A complete mechanism for the radiolysis of liquid pyridine is presented.     

Regional cerebral blood flow in cerebrovascular disease studied using N-isopropyl-p-(123I) iodoamphetamine

Twenty-one patients with cerebrovascular disease (5 with hemorrhage, 10 with infarction, 2 with TIA, 4 with motor disturbance of unknown cause) were studied using N-isopropyl-p-(123I)iodoamphetamine (123I-IMP) and single photon emission CT. In 3 of 5 cases with cerebral hemorrhage, perfusion defects were shown in and around the region of hematomas, furthermore, one of the cases with internal capsular hematoma, the perfusion defect extended to the cortical area corresponding to the neurological pathway. In one case with MCA infarction, the perfusion defect was greater and clearer than the low density area on X-ray computed tomography (CT). These results revealed the 123I-IMP study provides physiological information in contrast with X-ray CT which provides anatomical information. In 3 of 9 cases with multiple small deep hemispheric infarctions on X-ray CT, the perfusion to the basal ganglia was suspected to be decreased on 123I-IMP images. However, this visual findings was not definitive and, in fact, the diseased side was not always consistent with the clinical findings. For quantitative analysis, symmetrical regions of interest (ROIs) were constructed both basal ganglia and the ratio of average counts over the ROI to those over the whole slice was calculated. In the small infarction group, the mean +/- S.D. of the values was 0.89 +/- 0.09 in right and 0.89 +/- 0.08 in left. Although the values were not significantly different from those of normal subjects (0.99 +/- 0.02 in right, 0.97 +/- 0.03 in left), they distributed in the range less than normal in 5 of 9 cases. This method was thought to be useful and practical to evaluate the cerebral blood flow in basal ganglia of patients with deep hemispheric infarction.     

不同环境蔬菜中铅污染的研究

用原子吸收分光光度计石墨炉法分析了公路附近的蔬菜中铅的含量。结果表明,蔬菜中铅的含量还与其距离公路的远近有关,蔬菜与空气接触程度也有关;不同种类蔬菜中的铅污染有差异。     

Tuning of redox properties of iron and iron oxides via encapsulation within carbon nanotubes

We report the tuning of the redox properties of iron and iron oxide nanoparticles by encapsulation within carbon nanotubes (CNTs) with varying inner diameters. Raman spectroscopy was employed to investigate the interaction of the encapsulated nanoparticles with the CNTs. A red shift of the Fe-O mode is observed in the nanoparticles deposited on the outer CNT surfaces with respect to bulk Fe2O3. However, this mode is found to be stepwise blue-shifted with decreasing inner diameter in the CNT-encapsulated Fe2O3 nanoparticles, suggesting an enhanced interaction of Fe2O3 with the inner CNT surface as its curvature increases. The autoreduction of the encapsulated Fe2O3 is significantly facilitated inside CNTs with respect to the outside nanoparticles. Interestingly, it becomes more facile with decreasing CNT channel diameter as evidenced by temperature programmed reaction, in situ XRD, and Raman spectroscopy. The oxidation of encapsulated metallic Fe nanoparticles on the other hand is retarded in comparison to that of the outside Fe particles as shown by in situ XRD and gravimetrical measurements with an online microbalance. We attribute this tunable redox behavior of transition metal nanoparticles inside CNTs to a particular electronic interaction of the encapsulates with the interior CNT surface, which stabilizes the metallic state of Fe.     

An investigation of the electrocatalytic behaviour of gold in aqueous media

A survey was carried out on the electrocatalytic behaviour of gold, both for oxidation and reduction processes, mainly with regard to aqueous solutions of low pH. The results were interpreted in terms of the adatom-incipient hydrous oxide mediator mechanism of electrocatalysis; the important mediator for oxidation was considered to be a very low coverage Au(III) species which, as in base, can exist in two different forms. Agreement with regard to premonolayer formation potential values on changing from base to acid was excellent, providing that the process involved is assumed to exhibit a super-nernstian shift commonly observed with hydrous oxide systems. The mediation process is less effective with gold in acid as compared with base and with some organics the oxidation currents in acid exhibited significant decay with time under constant potential conditions. The reduction of persulphate was inhibited, apparently because of product adsorption at Au(I) cationic sites.     

Dynamics of free chains in polymer nanocomposites

The dynamics of entangled polymeric chains in a polymer filled with nanoparticles is studied by means of molecular dynamics simulations of a model system. The primary objective is to study to what extent the reptation of polymers not in direct contact with fillers is modified with respect to the neat material. To this end, two systems are considered: A regular filled material in which the filler-polymer affinity is controlled, and a system in which the beads in contact with the filler at the beginning of the production phase of the simulation are tethered to the filler surface. This second system represents the limit case of long polymer-filler attachment time. In this case attention is focused on the free chains of the melt. The dynamics in the two models is different. In the filled system uniform slowing down for all Rouse modes is observed. The effect varies monotonically with the filler-polymer affinity. Up to saturation, this behavior may be captured by usual models with an effective, affinity-dependent, friction coefficient. In the system with grafted chains, the free chain Rouse dynamics is identical to that in the neat material, except for the longest modes which are significantly slowed down. More interestingly, the dynamics of the free chains depends in a nonmonotonic way on the polymer-filler affinity, although the free chains do not come in direct contact with the filler. This effect is due to small changes in the structure of the polydisperse brush upon modification of the affinity. Specifically, the density of the brush and the amount of interpenetration of free and grafted chains depend on the filler-polymer affinity. The use of a reptation model with modified tube diameter to capture this behavior is discussed.     

Determination of betamethasone and triamcinolone acetonide by GC-NCI-MS in excreta of treated animals and development of a fast oxidation procedure for derivatisation of corticosteroids.

The use of corticosteroids in combination with other hormonal substances has long been known to result in increased mass gain with bovines. Practice has demonstrated, however, that even the single use of a glucocorticoid may result in growth promoting effects. In addition to the popular dexamethasone, more recently other corticosteroids have also been misused for fattening purposes. The first part of this study deals with the detection of two of them, namely betamethasone and triamcinolone acetonide. Betamethasone was administered orally to a cow at a dose of 50 mg d-1 for 5 d, then later the same cow was injected intramuscularly with a dose of 50 mg of betamethasone dipropionate. Excretion in urine and faeces was followed with both HPLC-enzyme immunoassay and a previously described method based on negative chemical ionization mass spectrometry (NCI-MS) after oxidation. For the triamcinolone acetonide study a cow was treated with 50 mg d-1 of the drug during a 7 d period. Excretion in faeces was followed with GC-NCI-MS. As triamcinolone acetonide is resistant to the previously described oxidation procedure, however, a hydrolysis step had to be introduced prior to oxidation. In addition to this specific modification necessary for triamcinolone acetonide, in a subsequent part of this study the original oxidation procedure with pyridinium chlorochromate was re-investigated especially to shorten the procedure. With the introduction of potassium dichromate the reaction time could be decreased from 3 h to 10 min.     

BAB‐random‐C Monomer Sequence via Radical Terpolymerization of Limonene (A), Maleimide (B), and Methacrylate (C): Terpene Polymers with Randomly Distributed Periodic Sequences

A naturally abundant terpene, limonene (A), was radically polymerized with a maleimide derivative (B) and methacrylate (C) in a fluorinated alcohol to give terpolymers with unprecedented BAB‐random‐C sequences in which the BAB monomer sequence was randomly copolymerized with a C unit. In each binary system, limonene was hardly copolymerized with methacrylate while it was efficiently copolymerized with maleimide to result in a 1:2‐alternating BAB periodic sequence, in part due to the penultimate effects and hydrogen‐bonding interactions with fluoroalcohol. Methacrylate and maleimide were randomly copolymerized to give copolymers rich in methacrylate units with minimal amounts of maleimide–maleimide sequences. Their terpolymerization resulted in a BAB‐r‐C sequence as a consequence of the selective BAB polymerization between limonene and maleimide, the random copolymerization between methacrylate and maleimide, and the lack of copolymerization between limonene and methacrylate.     

Action spectra for photoinduced inactivation of bacteriophage T7 sensitized by 8-methoxypsoralen and angelicin

The action spectrum (240-300 nm) for photoinactivation of unsensitized phage T7 and the action spectra (310-380 nm) for photoinactivation of phage T7 sensitized with 8-methoxypsoralen (8-MOP) and angelicin were measured by an automated method. For unsensitized phage T7 the action spectrum is in good agreement with the absorption spectrum. For sensitization with angelicin the action spectrum is similar to the absorption spectrum, but for sensitization with 8-MOP the spectra are different. The agreement between the T7 absorption and action spectra in the far-UV region is due to photodamage of DNA, leading to phage inactivation. The similarity in the action and absorption spectra in the near-UV region for sensitization with angelicin seems to be in accordance with the monofunctional photobinding of angelicin to DNA. The action spectrum for sensitization with 8-MOP has a maximum at about 320 nm and this suggests that, in addition to the monoadducts, the biadducts play a role in the inactivation of phage T7. Taking the number of bound furocoumarin molecules into consideration, the quantum efficiencies were estimated. Furocoumarin increases the quantum efficiency in the near-UV region and the values are similar to those obtained in far-UV light without psoralens.     

Patch-distribution effect on diffusion-limited process in dilute suspension of partially active spheres

The normalized overall rate constant, kp/kf for diffusion-limited processes in a dilute suspension of spheres, partially covered with active patches of varying distribution states, is studied with sped-up Brownian dynamic simulations. A dimensionless separation index Is is defined to quantify the characteristics of patch distribution on the sphere surfaces, with values of 0 and 1 corresponding to the states of the most compact and loosest patch distributions, respectively. Remarkably, the normalized overall rate constant is found to strongly correlate with the dimensionless separation index at fixed patch coverage fcover exhibiting a positive, linear relationship. In addition, the slope of the kp/kf vs Is line, a measure of sensitivity of kp/kf to variation in the separation state of the distributed patches, is found to depend on patch coverage and patch size. This sensitivity exhibits a maximum value with respect to an increase in patch coverage, and the magnitude of the maximum sensitivity decreases with increasing patch size. The patch coverage, at which the maximum sensitivity occurs, increases with increasing patch size.     

A single HBsAg DNA vaccination in combination with electroporation elicits long-term antibody responses in sheep

Vaccines continue to be the most cost effective method to reduce the burden of disease in both human and animal health. However, there is a need to improve the duration of immunity following vaccination, since maintenance of protective levels of antibody in serum or the ability to rapidly respond upon re-exposure (memory) is critical if vaccines are to provide long-term protective immunity. The purpose of this experiment was to test the duration of antibody responses and the ability to generate anamnestic responses following a single immunization with a DNA vaccine encoding hepatitis B surface antigen (HBsAg) delivered by a variety of routes. Sheep immunized with the conventional HBsAg subunit vaccine (Engerix-B) as well as sheep immunized with a HBsAg DNA vaccine, combined with electroporation, generated significant antibody responses that were sustained for 25 weeks after primary immunization. At 25 weeks, all experimental groups received a secondary immunization with the HBsAg subunit vaccine. Sheep that received a primary DNA immunization, in combination with electroporation, mounted an anamnestic response similar to the cohort immunized with the HBsAg subunit vaccine. In contrast, animals immunized with DNA vaccines administered without electroporation elicited no detectable memory response. The presence of immune memory was significantly correlated with the induction of a prolonged primary immune response. Thus, a single DNA vaccination, in combination with electroporation, approached the efficacy of the commercial subunit vaccine in the maintenance of long-term protective serum antibody titres and immune memory.