CE characterization of potential toxic labile iron in colloidal parenteral iron formulations using off-capillary and on-capillary complexation with EDTA

The present study describes the application of CZE to investigate the portion of labile iron in the following parenteral formulations: iron gluconate, iron saccharate, and iron dextran. Labile iron was detected as Fe(III)-chelate of EDTA at 246 nm. When EDTA was incubated with the formulations before electrophoresis, labile iron, or chelatable iron, respectively, was detected in all formulations, mostly in iron gluconate and iron saccharate. It was observed that the amount of iron released is time- and pH-dependent. In contrast, when EDTA was separately injected before the formulation sharp peaks of the Fe(III)-chelate were detected only after injection of iron gluconate. This type of labile iron can be described as "electrophoretically free" iron. CE provides thus a new method to characterize potential toxic, labile iron in parenteral iron formulations.     

Insight into the short-range structure of amorphous iron inositol hexaphosphate as provided by (31)P NMR and Fe X-ray absorption spectroscopy

Short-range structure and formation of amorphous aggregates of iron inositol hexaphosphate (iron phytate) were studied by broadline solid-state 31P NMR and Fe X-ray absorption spectroscopy. It was shown that bonds P-O-Fe with strong covalent character exist in solid substances. Iron in these substances is octahedrally coordinated by six oxygen atoms and further monodentatly bonded to three or four phosphorus atoms. In this way, iron generates -P-O-Fe-O-P- intermolecular connections. An insight into the formation of the network was obtained by studying structural changes in iron phytates with increasing concentrations of iron. It was shown that the solid network builds when at least four out of six phosphate groups per one phytic molecule bond to iron atoms and thus participate in the intermolecular connections. This leads to iron phytate with approximately two iron atoms per one molecule of phytate. When the concentration of iron in aggregates increases, the number of P-O-Fe bonds, and thus the number of phosphate groups that are bonded to iron, increases. Solid iron phytate with approximately four iron atoms per one molecule of phytate is almost saturated with iron. Its short-range structural properties can be explained well by a structure that is approaching an idealized model, in which each phosphate group is bonded to two iron atoms and each iron atom is bonded to three phosphorus atoms and is shared between two phytic molecules.     

Ion-exchanger colorimetry-VII Microdetermination of iron(II) and iron(III) in natural water

A trace method for iron, based on ion-exchanger colorimetry, has been developed. 1,10-Phenanthroline is used as the colour reagent for iron(II) and citrate as the masking reagent for iron(III). Total iron can be determined after reduction of iron(III) to iron(II) with hydroxylamine. It is possible to determine iron at mug/l.-levels in different oxidation states in natural waters.     

Changes of iron concentrations in skin and plasma of patients with hemochromatosis along therapy

Skin as a manageable organ can provide direct or indirect information of tissue iron overload resulting from inherited disorders as hemochromatosis. Patients with hemochromatosis were evaluated at three consecutive phases along the therapy programme. Nuclear microprobe techniques were used to assess skin iron and Total Reflection X-ray Fluorescence to determine the plasma iron concentrations. Results showed that iron pools were differently correlated at the three therapy phases. These variations highlighted the value of skin iron content to assess organ iron deposition and therapy efficacy. Skin iron content can be used for a better management of patients with iron overload pathologies.     

乙烷在金属铁表面还原NO的实验研究

温度300~1 100 ℃时,由程序控温电加热水平陶瓷管反应器在N₂气氛和模拟气氛下,对乙烷在金属铁表面还原NO的特性进行了实验研究。结果表明,乙烷在金属铁表面能够高效地还原NO。在N₂气氛中,温度高于900 ℃时,乙烷在金属铁表面的脱硝效率超过95%。在模拟烟气条件下,当温度超过900 ℃,且过量空气系数小于1.0时,乙烷在金属铁表面还原NO的效率能够达到90%以上。相同条件下,乙烷在金属铁表面脱硝效率高于甲烷的脱硝效率。SO₂对乙烷在金属铁表面还原NO的效率影响可以忽略。对反应后的铁样品的组分进行了XRD表征,在此基础上对反应机理进行了分析。结果表明,在模拟烟气条件下NO的还原通过乙烷的再燃脱硝和金属铁直接还原两个机理完成。金属铁直接还原NO时生成的氧化铁则被乙烷还原为金属铁,从而使得金属铁能够持续对NO进行直接还原。乙烷再燃还原NO的中间产物HCN被氧化铁氧化为N₂,同时氧化铁也被HCN还原为金属铁。这一过程增强了NO的持续还原反应,同时避免了在燃尽时HCN二次氧化重新生成NO,从而保证了较高的NO还原效率。     

Sequential determination of iron(II) and iron(III) in pharmaceutical by flow-injection analysis with spectrophotometric detection.

A flow injection procedure for the sequential spectrophotometric determination of iron(II) and iron(III) in pharmaceutical products is described. The method is based on the catalytic effect of iron(II) on the oxidation of iodide by bromate at pH = 4.0. The reaction was monitored spectrophotometrically by measuring the absorbance of produced triiodide ion at 352 nm. The activating effect for the catalysis of iron(II) was extremely exhibited in the presence of oxalate ions, while oxalate acted as a masking agent for iron(III). The iron(III) in a sample solution could be determined by passing through a Cd-Hg reductor column introduced in the FIA system to reduce iron(III) to iron(II), which allows total iron determination. Under the optimum conditions, iron(II) and iron(III) could be determined over the range of 0.05 - 5.0 and 0.10 - 5.0 microg ml(-1), respectively with a sampling rate of 17 +/- 5 h(-1). The experimental limits of detection were 0.03 and 0.04 microg ml(-1) for iron(II) and iron(III), respectively. The proposed method was successfully applied to the speciation of iron in pharmaceutical products.     

Speciation of iron using HPLC with electrochemical and flame-AAS detection

Summary A combined detection system for HPLC is presented, which consists of an electrochemical detector for iron(II) detection and an on-line flame-AAS detector for total iron. Detection limits are 5 ng iron for AAS and 1 ng iron(II) for electrochemical detection. Quantitative analysis of separated iron species is possible, even if iron(II) and iron(III) coelute. The proposed system is used for the investigation of coupled complexation and redox equilibria (e.g. Fe + oxalate). The application to fruit juice and wine is also presented. The predominant species found in apple juice are iron(II)-malate and iron(III)-citrate and in white wine iron(II)- and iron (III)-tartrates.     

含铁蛋白介导的铁转运分子机制

铁是生命体必需的微量元素,因为它是一些重要功能酶的协同因子。这些功能酶有着广泛的功能,从呼吸作用到核酸的复制。但是,当铁含量多于细胞稳态的时候,它将产生对机体有毒的羟基。生物体已经发展了自身的调控机制,包括铁的摄取,存储和输出来控制细胞内的铁处于平衡态。二价阳离子转运蛋白,铁输出蛋白和hephaestin参与小肠吸收,转铁蛋白和转铁蛋白受体参与铁的摄取和转运,铁蛋白可以存储铁,铁调控蛋白的功能是调节铁代谢。这篇文章综述着重阐述了含铁蛋白介导的铁传递机制。     

照相明胶中铁的化学形态研究

利用凝胶层析-电热石墨管炉原子吸收光谱法对照相明胶中铁的化学形态进行了研究。发现明胶中的铁主要与蛋白结合为大分子,同时也有少量小分子量蛋白铁和游离铁。当向明胶样品申加入微量无机铁盐后,铁仍以游离态存在,未与蛋白结合,因而随着明胶中铁含量明显降低,外界铁的污染必须加以特别注意。在照相乳剂制备中必须同时考虑明胶中铁总量及其存在的化学形态。     

Hexacyanoferrate(III) as a mediator in the determination of total iron in potable waters as iron(II)-1,10-phenanthroline at a single-use screen-printed carbon sensor device

Hexacyanoferrate(III) was used as a mediator in the determination of total iron, as iron(II)-1,10-phenanthroline, at a screen-printed carbon sensor device. Pre-reduction of iron(III) at −0.2 V versus Ag/AgCl (1 M KCl) in the presence of hexacyanoferrate(II) and 1,10-phenanthroline (pH 3.5-4.5), to iron(II)-1,10-phenanthroline, was complete at the unmodified carbon electrode surface. Total iron was then determined voltammetrically by oxidation of the iron(II)-1,10-phenanthroline at +0.82 V, with a detection limit of 10 μg l⁻¹.In potable waters, iron is present in hydrolysed form, and it was found necessary to change the pH to 2.5-2.7 in order to reduce the iron(III) within 30 s. A voltammetric response was not found at lower pH values owing to the non-formation of the iron(II)-1,10-phenanthroline complex below pH 2.5.Attempts to incorporate all the relevant reagents (1,10-phenanthroline, potassium hexacyanoferrate(III), potassium hydrogen sulphate, sodium acetate, and potassium chloride) into a modifying coated PVA film were partially successful. The coated electrode behaved very satisfactorily with freshly-prepared iron(II) and iron(III) solutions but with hydrolysed iron, the iron(III) signal was only 85% that of iron(II).     

十八烷基胺在铁上成膜结构和耐腐蚀性研究

十八烷基胺(ODA)应用于热力设备停用保护技术在国外开发较早[1－3],国内电厂这二年来应用该技术也日益增多,但由于基础研究做得较少,使用效果受到影响.1996年以来我们对ODA的成膜条件和机理进行了一些研究[4－6],本文利用交流阻抗、俄歇电子能谱、红外镜反射光谱、光电化学等方法对ODA的成膜结构和耐蚀性进行探讨,同时介绍ODA在电厂的应用情况.1实验实验材料为DT-4型纯铁.样品制备及交流阻抗测试见文献[4－6].　　俄歇能谱(AES)Perkin-ElmerPHI550ESCA/SAM.实验在机械工业部上海材料研究所进行.　　红外镜反射(SR)Bio-R…     

Synthesis and Characterization of Iron Nanowires

The iron nanowires can be fabricated via the process in which sodium borohydride reduces iron salts in external magnetic field. The iron nanowires are found to be covered by passivated layers of iron oxide which prevent the oxidation of iron nanowires. In this process, the boron will include in iron nanowires. The average length and diameter of iron nanowires is around 1.2 micrometers and 60 nanometers, respectively. According to ICP results, the contents of B and Fe are about 1.98 wt% and 87.04 wt%, respectively, in iron nanowires. A wide variety of equipment is used to investigate the morphological, microchemical, and structural characteristics of the newly synthesized iron nanowires ––– e.g., XRD, FE‐SEM, HR‐TEM, VSM and XANES. XANES analysis indicates the boron in iron nanowires exists in the form of B₂O₃. The saturation magnetization and the coercive force of iron nanowires are 157.93 emu/g and 9.74 Oe, respectively. In‐situ images of synthesized iron nanowires during reduction process in magnetic field are observed by NSRRC transmission X‐ray microscope. Thus, this study develop a novel process to produce iron nanowires with large quantitates and can control its length and diameter by various the concentration of precursors for various applications.     

Mitochondrial Iron Metabolism: The Crucial Actors in Diseases

Iron is a trace element necessary for cell growth, development, and cellular homeostasis, but insufficient or excessive level of iron is toxic. Intracellularly, sufficient amounts of iron are required for mitochondria (the center of iron utilization) to maintain their normal physiologic function. Iron deficiency impairs mitochondrial metabolism and respiratory activity, while mitochondrial iron overload promotes ROS production during mitochondrial electron transport, thus promoting potential disease development. This review provides an overview of iron homeostasis, mitochondrial iron metabolism, and how mitochondrial iron imbalances-induced mitochondrial dysfunction contribute to diseases.     

Mechanism of binding of iron to potential therapeutic chelating agents

To aid in designing new therapeutic iron chelating agents, the mechanism of iron binding to prototypic heterocyclic carboxaldehyde thiosemicarbazones has been studied. Based on molecular orbital and spectroscopic studies, iron (II) is found to bind in a covalent manner, while iron(III) seems to interact ionically. However, with both iron(II) and iron(III), chelate formation is dependent on charge interaction between the metal and the coordinating atoms of the ligand.     

铁缺乏症对婴幼儿智能发育的影响

为分析铁缺乏症(IDD)对婴幼儿智能发育的影响，随机抽取了6个月至3岁婴幼儿200例，按有否铁缺乏分组，比较了其与智能的关系。结果表明，铁缺乏症检出率为17．5％，铁缺乏组婴幼儿智能发育商(DQ)明显下降，与正常组比较差异有显著性，铁缺乏程度越重，DQ值越低。可见铁缺乏症对婴幼儿大脑发育造成不良影响，对该症无贫血阶段及轻度缺铁性贫血期(IDA)应予重视。     

甲烷在金属铁及氧化铁表面还原NO的研究

在程序控温电加热水平陶瓷管反应器、N₂气氛和模拟烟气气氛及300~1 100℃时,对甲烷在金属铁及其氧化铁表面还原NO的特性进行了实验研究。为使甲烷在脱硝反应后完全燃尽以及脱硝反应过程生成的CO等中间产物完全燃尽,在第一段加热炉后串联了第二段加热炉,补充氧气,实现燃尽。结果表明,甲烷在金属铁及氧化铁表面能够高效地还原NO。在N₂气氛中,在900℃以上温度范围内甲烷在金属铁表面的脱硝效率超过95%,与甲烷在氧化铁表面的脱硝效率差别很小。在模拟烟气条件下,当过量空气系数小于1.0时,在900℃以上时,甲烷在金属铁和氧化铁表面的脱硝效率都能超过90%,且未燃尽和燃尽两种条件下NO的还原率相差不大。NO同时通过金属铁的直接还原和甲烷的再燃还原两种反应机理脱除。而甲烷则通过还原氧化铁为金属铁,从而使金属铁直接还原NO可持续进行。同时,甲烷再燃反应的中间产物HCN/NH₃等被氧化铁还原,从而使燃尽后的脱硝效率不下降。研究结果表明,甲烷和金属铁或氧化铁在富燃料条件下可有效地还原NO。     

Catechol releases iron(III) from ferritin by direct chelation without iron(II) production

It has been traditionally considered that catechols release iron from ferritin by reduction to iron(II), which diffuses through the ferritin channels into the intracellular milieu where it participates in the Fenton reaction, producing highly toxic hydroxyl radicals. However, in the present work we have proved that the mechanism of the release of iron from ferritin by catechol does not take place by iron(II) reduction but by direct iron(III) chelation and therefore without iron(II) production. A possible extension of these findings to other catechols is discussed on the basis of the stability with respect to the internal redox reaction of the iron(III)-catechol complexes.     

Photo‐oxidative Stress Impacts the Expression of Genes Encoding Iron Metabolism Components in Chlamydomonas†

Chlamydomonas, like other organisms, regulates iron assimilation very tightly through differential expression of iron assimilation components. Nevertheless, in the presence of excess iron, cells do overaccumulate iron but without an evident phenotype. As iron toxicity is attributed to reactive oxygen species, we tested the impact of photon flux density (PFD) on cells with increased iron content. We noted that growth at >500 μmol m^?2 s^?1 is inhibited as iron content of the medium is increased, suggesting that high light exacerbates the systems of iron toxicity and vice versa. Cells grown in high light selectively down‐regulate the abundance of iron assimilation components, ferroxidase and FEA1, and storage protein ferritin1. At the RNA level, the abundance of ferroxidase (FOX1), iron reductase (FRE1), iron assimilatory protein (FEA1) and ferritin (FER1) mRNAs is also decreased. The time course of the response to high light compared to the response to Rose Bengal and H₂O₂ treatments suggests that both singlet oxygen and H₂O₂ may be implicated in the high light response. This hypothesis is supported by the recapitulation of some but not all of the high light responses in the carotenoid‐deficient, high light–sensitive npq1lor1 strain. We conclude that responses to iron nutrition and PFD are connected, and the determination of an optimum for photosynthetic growth for each is dependent on the other. This work defines a fourth stage of iron nutrition in Chlamydomonas, the iron excess situation, which can be molecularly and physiologically distinguished from the iron‐limited, iron‐deficient and iron‐replete stages, described previously.     

Demonstration of the Heterolytic O?O Bond Cleavage of Putative Nonheme Iron(II)?OOH(R) Complexes for Fenton and Enzymatic Reactions

One‐electron reduction of mononuclear nonheme iron(III) hydroperoxo (Fe^III OOH) and iron(III) alkylperoxo (Fe^III OOR) complexes by ferrocene (Fc) derivatives resulted in the formation of the corresponding iron(IV) oxo complexes. The conversion rates were dependent on the concentration and oxidation potentials of the electron donors, thus indicating that the reduction of the iron(III) (hydro/alkyl)peroxo complexes to their one‐electron reduced iron(II) (hydro/alkyl)peroxo species is the rate‐determining step, followed by the heterolytic O O bond cleavage of the putative iron(II) (hydro/alkyl)peroxo species to give the iron(IV) oxo complexes. Product analysis supported the heterolytic O O bond‐cleavage mechanism. The present results provide the first example showing the one‐electron reduction of iron(III) (hydro/alkyl)peroxo complexes and the heterolytic O O bond cleavage of iron(II) (hydro/alkyl)peroxo species to form iron(IV) oxo intermediates which occur in nonheme iron enzymatic and Fenton reactions.     

Effect of confinement in carbon nanotubes on the activity of Fischer-Tropsch iron catalyst

Following our previous findings that confinement within carbon nanotubes (CNTs) can modify the redox properties of encapsulated iron oxides, we demonstrate here how this can affect the catalytic reactivity of iron catalysts in Fischer-Tropsch synthesis (FTS). The investigation, using in situ XRD under conditions close to the reaction conditions, reveals that the distribution of iron carbide and oxide phases is modulated in the CNT-confined system. The iron species encapsulated inside CNTs prefer to exist in a more reduced state, tending to form more iron carbides under the reaction conditions, which have been recognized to be essential to obtain high FTS activity. The relative ratio of the integral XRD peaks of iron carbide (Fe(x)C(y)) to oxide (FeO) is about 4.7 for the encapsulated iron catalyst in comparison to 2.4 for the iron catalyst dispersed on the outer walls of CNTs under the same conditions. This causes a remarkable modification of the catalytic performance. The yield of C5+ hydrocarbons over the encapsulated iron catalyst is twice that over iron catalyst outside CNTs and more than 6 times that over activated-carbon-supported iron catalyst. The catalytic activity enhancement is attributed to the effect of confinement of the iron catalyst within the CNT channels. As demonstrated by temperature-programmed reduction in H2 and in CO atmospheres, the reducibility of the iron species is significantly improved when they are confined. The ability to modify the redox properties via confinement in CNTs is expected to be of significance for many catalytic reactions, which are highly dependent on the redox state of the active components. Furthermore, diffusion and aggregation of the iron species through the reduction and reaction have been observed, but these are retarded inside CNTs due to the spatial restriction of the channels.