Effect of Cu2+ Ions and Buffering Capacity on Smectite Microstructure and Performance

Smectite is usually used as buffer clay for contaminant of high level nuclear waste canisters. Corrosion of the canisters will expose the buffer clay to Cu2+ ions as one of the corrosion products. This study investigates the effect of Cu2+ cations in a smectite, with and without addition of sodium carbonate in the clay, on its consolidation behavior and transmission characteristics. Characterization experiments conducted in the study included determination of changes in the buffering capacity and permeability properties of the clay in relation to the presence of varying concentrations of Cu2+, and consolidation experiments. Double-layer swelling forces and buffering capacity are seen to be dominant factors in the performance of the clays—apparently through their influence on formation and restructuring of microstructures in the overall smectite clay mixtures.     

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In order to understand the effects of various iron oxides on the properties of melts, viscosity, density as well as sulphide capacities of slag system containing FeOx were summarized and discussed. It is indicated that either thermophysical or thermochemical properties would be modified accordingly with the valence change of iron oxides. Fe2+ and Fe3+ have different functions in slag. Fe2+ existed as a network-breaker, which resulted in the decreasing of viscosity and increasing of sulphide capacities with increasing addition of FeO. However, Fe3+ commonly would occupy the tetrahedron and octahedron positions, and play a network-former role, consequently, cause the viscosity of melts increasing etc. Direct investigations of slag structure or valence state of iron in the melt also support the regular patterns derived indirectly from the various physical-chemical properties. Meanwhile, these patterns of slag system including iron oxides also offer a good reference to the study of other transition melt oxides in slag system.     

1723K下熔渣中Ni~(2+)和Fe~(2+)离子共存时的电化学行为

利用MgO部分稳定的ZrO_2固体电解质管集成构建以Pt,O_2(空气)|ZrO_2作为参比电极的新型可控氧流电解池,采用循环伏安CV、方波伏安SWV、恒电位电解PE等方法,并结合热力学计算与显微观察、能谱分析,研究1 723K高温下SiO_2-CaO-MgO-Al_2O_3熔渣中共存的Ni~(2+)、Fe~(2+) 离子在Ir电极上的电化学行为。结果表明:熔渣系中FeO与NiO之间存在较弱的相互作用,但镍离子以Ni~(2+)存在,铁离子基本以Fe~(2+) 存在。进行方波伏安分析时,Ni~(2+)、Fe~(2+) 离子的还原峰电流对频率呈现不同的规律。Ni~(2+)在Ir电极上的电化学还原是扩散控制的一步两电子转移反应过程;Fe~(2+) 到Fe的电化学还原也是一步两电子转移反应过程,但Fe~(2+) 的还原明显受到Ni~(2+)还原的影响。基于循环伏安法,计算得到NiO、FeO的质量分数分别为3%、5%的熔渣中Ni~(2+)离子在1 723K下的扩散系数为(9.2±0.2)×10-6cm2/s。     

Reversible metabolic myopathy in biotinidase deficiency: its possible role in causing hypotonia

A 5-year-old girl diagnosed with biotinidase deficiency at 9 months of age demonstrated limb and axial hypotonia which improved on biotin therapy. In this patient, electromyographic (EMG) studies prior to treatment were compatible with a mild myopathic process. Serial EMGs performed on biotin therapy demonstrated a gradual resolution of the myopathy. This is the first documented case of a reversible myopathy in a patient with biotinidase deficiency, which may contribute to the clinical findings of hypotonia.     

Variation of Fe3+/Fe2+ and Cu2+/Cu+ equilibrium with basicity of oxide melts

Oxidation-reduction equilibrium experiments were conducted with Li₂O-CaO-Al₂O₃-ZnO-SiO₂-B₂O₃ melts containing small concentrations of either copper oxide or iron oxide. The results indicated that, for oxide melts containing relatively large proportions of amphoteric oxides, i.e., Al₂O₃ and ZnO, the ratios lcub;(Cu²⁺)/(Cu⁺)P _{O 2} ^1/4rcub; and lcub;(Fe³⁺)/(Fe²⁺)P _{O 2} ^1/4rcub; decreased with an increase in basicity. With further increase in basicity, however, these ratios became independent of basicity. For very basic melts, the ratios increased with an increase in basicity. These variations of lcub;(Cu²⁺)/(Cu⁺)P _{O 2} ^1/4rcub; and lcub;(Fe³⁺)/(Fe²⁺)P _{O 2} ^1/4rcub; can be interpreted in terms of the optical basicity of the oxide melts and are consistent with the following general expressions for the red-ox equilibria within acidic and relatively basic melts, respectively: M ⁿ⁺+(1/4)O₂=M⁽ⁿ⁺¹⁾⁺+(1/2)O²⁻ M ⁿ⁺+(1/4)O₂+(3/2)O²⁻=MO₂ ⁽³⁻ⁿ⁾ and M ⁿ⁺+(1/4)O₂=(3/4)M⁽ⁿ⁺¹⁾⁺+(1/4)MO₂ ⁽³⁻ⁿ⁾     

High-frequency brain activity: its possible role in attention, perception and language processing

Coherent high-frequency neuronal activity has been proposed as a physiological indicator of perceptual and higher cognitive processes. Some of these processes can only be investigated in humans and the use of non-invasive recording techniques appears to be a prerequisite for investigating their physiological substrate in the healthy human brain. After addressing methodological issues in the non-invasive recording of high-frequency responses, we summarize studies indicating co-occurrence of neuronal synchrony of single cells exhibiting rhythmic activity at high frequencies, oscillations in the local field potential and dynamics in high frequencies recorded using high-resolution electroencephalography (EEG) and magnetoencephalography (MEG). We then review EEG and MEG studies of attention, perception, and language processing in humans indicating that dynamics in the high-frequency range > 20 Hz reflect specific cognitive processes. Types of high-frequency (HF) activity can be distinguished according to their latency after stimulus onset, stimulus-locking, cortical topography and frequency. There appears to be a systematic relationship between specific cognitive processes and types of HF activity. The findings are related to recent theories about the generation of HF activity and their possible role in binding of stimulus features. Dynamics of HF cortical activity reflecting higher cognitive processes can be accounted for based on the assumption that the elements of cognitive processing, e.g. visual objects and words, are organized in the brain as distributed neuronal assemblies with defined cortical topographies generating well-timed spatio-temporal activity patterns.     

循环伏安法测定溶液中Fe3+和Fe2+浓度比

采用循环伏安法（CV）测定铁泥制备Fe3O4过程中Fe3+与Fe2+浓度比值的变化,为该工艺过程提供方便、快捷的监测方法。在实验条件下,溶液中的Fe3+与Fe2+组成可逆的氧化还原体系,产生一对峰形良好的氧化还原峰。对影响峰电流的扫描速度、pH值及干扰离子等因素进行考察,结果表明,扫描速度在0.002~0.01 V/s、pH在1.5~2.5时对氧化峰电流及还原峰电流没有影响;溶液中存在的SO42-离子在实验范围内对体系基本无干扰。Fe3+的浓度在0.000 8～0.008 4 mol/L呈线性关系,相关系数为0.999 9,相对标准偏差(n=7)在 0.70%~2.0%之间。该法与标准重铬酸钾滴定法对比,相对误差为1.7%。     

Ga3+ as a functional substitute for Fe3+: preparation and characterization of the Ga3+Fe2+ and Ga3+Zn2+ forms of bovine spleen purple acid phosphatase

A general method has been developed that allows the specific substitution of both iron atoms in the enzyme bovine spleen purple acid phosphatase (BSPAP), which possesses a dinuclear iron center at the active site. The approach is demonstrated by the preparation and characterization (atomic absorption spectrometry, enzyme kinetics, optical spectroscopy, and electron paramagnetic resonance spectroscopy) of two metal-substituted forms in which the ferric iron has been replaced by Ga3+: Ga3+Fe2+-BSPAP and Ga3+Zn2+-BSPAP. Both forms are colorless but exhibit enzymatic activity comparable to that of the native Fe3+Fe2+-BSPAP. Small but consistent changes in kinetics parameters and pH profiles were detected both upon substitution of Fe3+ by Ga3+ and upon substitution of Fe2+ by Zn2+. These results constitute the first evidence that the diamagnetic Ga3+ ion can serve as a functional analogue of Fe3+ in an enzyme, and suggest a novel approach for the study of the role of Fe3+ in other iron enzymes.     

Inhibition of myocardial L- and T-type Ca2+ currents by efonidipine: possible mechanism for its chronotropic effect

Effects of efonidipine, a dihydropyridine phosphonate Ca2+ channel antagonist, on the guinea-pig heart were compared with those of nifedipine. In the sino-atrial node, 1 microM efonidipine produced increase in cycle length accompanied by prolongation of the phase 4 depolarization which was not prominent with 0.1 microM nifedipine. In ventricular myocytes, both efonidipine and nifedipine produced inhibition of the L-type Ca2+ current, nifedipine being tenfold more potent than efonidipine. Efonidipine also inhibited the T-type Ca2+ current at higher concentrations but nifedipine did not. Both Ca2+ channel antagonists had no or only a weak effect on K+ currents. In addition, 40 microM Ni2+, which selectively inhibited the T-type Ca2+ current, had no effect on myocardial Ca2+ transients and contractile force. In conclusion, efonidipine was shown to have inhibitory effects on both L- and T-type Ca2+ currents, which may contribute to its high negative chronotropic potency.     

Correlation of radiologic and pathologic-anatomical findings in dust-induced pneumoconiosis in former coal miners

The ILO classification of small and large opacities is the basis for the compensation of patients with pneumoconiosis. In order to validate the radiological findings, we compared the ILO classification with the gradings of pneumoconiosis in the post mortem investigation (n = 126). An ILO classification of 1/0 used as the threshold value for accepting the diagnosis of a pneumoconiosis was 100% sensitive with a specificity of 2%. With a value of 2/3 the sensitivity decreased to 60% and specificity increased to 74%. The grading of large opacities in the radiograph correlated well with the post mortem findings (rs = 0.71; p < 0.001). For accepting the diagnosis pneumoconiosis from the radiograph alone a threshold value of 1/0 is not specific. The ROC-plot revealed that specificity reached acceptable levels with an ILO classification of at least 2/3.     

Phosphorylation of glycerol and dihydroxyacetone in Acetobacter xylinum and its possible regulatory role

Extracts of Acetobacter xylinum catalyze the phosphorylation of glycerol and dihydroxyacetone (DHA) by adenosine 5'-triphosphate (ATP) to form, respectively, L-alpha-glycerophosphate and DHA phosphate. The ability to promote phosphorylation of glycerol and DHA was higher in glycerol-grown cells than in glucose- or succinate-grown cells. The activity of glycerol kinase in extracts is compatible with the overall rate of glycerol oxidation in vivo. The glycerol-DHA kinase has been purified 210-fold from extracts, and its molecular weight was determined to be 50,000 by gel filtration. The glycerol kinase to DHA kinase activity ratio remained essentially constant at 1.6 at all stages of purification. The optimal pH for both reactions was 8.4 to 9.2. Reaction rates with the purified enzyme were hyperbolic functions of glycerol, DHA, and ATP. The Km for glycerol is 0.5 mM and that for DHA is 5 mM; both are independent of the ATP concentration. The Km for ATP in both kinase reactions is 0.5 mM and is independent of glycerol and DHA concentrations. Glycerol and DHA are competitive substrates with Ki values equal to their respective Km values as substrates. D-Glyceraldehyde and l-Glyceraldehyde were not phosphorylated and did not inhibit the enzyme. Among the nucleotide triphosphates tested, only ATP was active as the phosphoryl group donor. Fructose diphosphate (FDP) inhibited both kinase activities competitively with respect to ATP (Ki= 0.02 mM) and noncompetitively with respect to glycerol and DHA. Adenosine 5'-diphosphate (ADP) and adenosine 5'-monophosphate (AMP) inhibited both enzymic activities competitively with respect to ATP (Ki (ADP) = 0.4 mM; Ki (AMP) =0.25 mM). A. xylinum cells with a high FDP content did not grow on glycerol. Depletion of cellular FDP by starvation enabled rapid growth on glycerol. It is concluded that a single enzyme from A. xylinum is responsible for the phosphorylation of both glycerol and DHA. This as well as the sensitivity of the enzyme to inhibition by FDP and AMP suggest that it has a regulatory role in glycerol metabolism.     

Respiratory symptoms and pulmonary function in coal miners: looking into the effects of simple pneumoconiosis

Most soil quality guidelines do not distinguish among the various forms of metals in soils; insoluble, nonreactive, and nonbioavailable forms are deemed as hazardous as highly soluble, reactive, and toxic forms. The objective of this study was to better understand the long-term effects of copper on microorganisms in relation to its chemical speciation in the soil environment. Carbon mineralization processes and the global structure of different microbial communities (fungi, eubacteria, actinomycetes) are still affected after more than 50 years of copper contamination in 20 soils sampled from two different agricultural sites. The microbial respiration lag period (LP) preceding the beginning of mineralization process increases with the level of soil copper contamination and is not significantly affected by other environmental factors such as soil pH and soil organic matter (SOM) content. The total copper concentration showed the best correlation with the LP when each site is considered separately. However, when considering the whole set of data, soil solution free Cu2+ activity (pCu2+) is the best predictor of Cu toxicity determined by LP (quite likely because pCu2+ integrates the soil physicochemical variability). The maximum mineralization rate (MMR), even if well correlated with the pCu2+, appears not to be a good biomonitor of copper contamination in soils since it is highly sensitive to soil characteristics such as SOM content. This study emphasizes the importance of the physicochemical properties of the environment on soil heavy metal toxicity and on soil toxicological measurements. These properties must be characterized in soil toxicological studies with respect to (1) their interactions with heavy metals, and (2) their direct impact on the selected biological test. The measurement of pCu2+ to characterize the level of soil contamination and of lag period as a bioindicator of metal effects in the soil are recognized as useful tools for the evaluation of the biological quality of soils.     

交联羧甲基壳聚糖的合成及其对Pb2+、Cd2+和Co2+的吸附行为

在超声波辐射作用下,以非质子溶剂二甲亚砜为溶剂,制备了新型吸附剂交联羧甲基壳聚糖。利用X-射线光电子能谱、傅里叶红外光谱等分析手段对样品进行了测试和表征。以Pb²⁺、Cd²⁺和Co²⁺为吸附对象,考察了溶液初始浓度、吸附时间、酸度等因素对吸附过程的影响。等温线实验表明Langmuir吸附模型适合模拟金属离子在交联羧甲基壳聚糖表面的吸附过程,说明金属离子在交联羧甲基壳聚糖表面的吸附为单分子层吸附,交联羧甲基壳聚糖对Pb²⁺、Cd²⁺和Co²⁺的最大吸附容量分别为282.49mg/g、328.95mg/g和134.41mg/g。动力学实验表明,准二级方程适合描述此吸附过程。     

Correlation of radiologic and pathologic-anatomical findings in dust-induced pneumoconiosis in former coal miners]

Anecdotal evidence from several ENT departments suggests that pain following tonsillectomy is worst on the second and/or third days after surgery. This study tests this hypothesis. A pilot study with 19 subjects suggested this theory might well be true. A fuller study was then carried out on 91 subjects with standardised surgical and anaesthetic techniques, and standardised analgesia for five days postoperatively. Pain on the second and third postoperative days was compared with that eight hours after the operation and on the first, fourth and fifth postoperative days. No statistically significant difference was found. There is increasing pressure for early discharge from hospital after surgery. If pain following tonsillectomy is not going to become worse at home, this will tend to make early discharge more acceptable to patients.     

Canine bronchial sustained contraction in Ca2+-free medium: role of intracellular Ca2+

We evaluated whether cartilage was a source of Ca2+ and the possible role of Ca2+ recycling in the sustained bronchial contraction (SBC) induced by carbachol (Cch) in Ca2+-free medium. Canine first-order bronchi were studied with cartilage and epithelium (+CAR + EPI) and without these structures individually (-CAR + EPI and +CAR - EPI) or together (-CAR - EPI). After cartilage removal (-CAR - EPI or -CAR + EPI) Cch produced a transient contraction in Ca2+-free medium. Removal of the epithelium alone had minor effects on the magnitude of the SBC but increased the effect of removal of cartilage to diminish the SBC. Bronchial strips with cartilage were able to respond to Cch with lower Ca2+ concentrations (10-100 microM) than could dissected preparations. Preincubation with BAY K 8644 (30-1000 nM) or 60 mM KCl or -CAR - EPI tissues converted the transient contractions to Cch in Ca2+-free medium to sustained contractions. In microelectrode studies, 50 nM Cch induced membrane oscillations in solutions with 2.5 mM Ca2+ in bronchial preparations, plus or minus cartilage, and in undissected tissues in Ca2+-free medium but not in -CAR - EPI tissues. Preincubation with 1 microM BAY K 8644 in Ca(2+)-free medium restored these oscillations in -CAR - EPI tissues. The release of 45Ca2+ from cartilage was too rapid to provide a reservoir of Ca2+ to support multiple SBCs in Ca2+-free medium. Moreover, in the Ca2+-free medium (with 10 nM Ca2+ after tissue +CAR + EPI incubation) excitatory junction potentials rapidly disappeared. Addition of 1 microM nifedipine or 1 mM EGTA during the SBC of +CAR + EPI tissues produced complete relaxation. A transient contraction to Cch occurred with prior addition of nifedipine. Inhibition of the sarcoplasmic reticulum Ca2+ pump by tissue incubation with cyclopiazonic acid (CPA; 10 microM), or briefly with 1 mM EGTA significantly diminished the SBC induced by Cch in Ca2+-free medium. CPA and EGTA together abolished the Cch-induced SBC. Thus, cartilage plays a more complex role than as a Ca2+ reservoir to support the SBC induced by Cch in Ca2+-free solution; its removal affects the process supporting SBCs involving intracellular Ca2+ storage and Ca2+ entrance through voltage-dependent channels.     

Macrophage-fibroblast interaction and its possible role in regulating collagen metabolism during wound healing

The role of macrophages in the resorption of denatured collagen in the wound tissue was demonstrated by transmission and scanning electron microscopy investigation. Tight cell contacts between the macrophages and fibroblasts in the granulation tissue preceded active collagen synthesis and fibrillogenesis. A hypothesis was suggested according to which these contacts played an important role in the transfer of specific signals for the initiation of collagen biosynthesis; collagen decomposition products were considered as the actual signals, thus connecting the collagen catabolism and biosynthesis. Such a feed-back mechanism probably served as an integral part of the general hemostasis regulating the growth of connective tissue.     

Thermodynamics of iron oxide in Fe x O-dilute CaO + Al2O3 + MgO + Fe x O slags at 1873 K

In order to determine the ferrous and ferric ion capacities: 3