Microanalytical method development for Fe, Cu and Zn determination in colorectal cancer cells

Microanalytical methods suitable for the determination of Fe, Cu in HT-29 (human colon adenocarcinoma) cells treated with different iron compounds (Fe(II) sulfate, Fe(III) chloride, Fe(III) citrate and Fe(III) transferrin) and cultured in medium supplemented or not with 10% (v/v) fetal calf serum (FCS) by total reflection X-ray fluorescence spectrometry (TXRF) and simultaneous graphite furnace atomic absorption spectrometry (GF-AAS) were developed. The developed TXRF method was also suitable for Zn determination in the samples. The main advantage of the proposed methods is the execution of all sample preparation steps following incubation and prior to the elemental analysis in the same Eppendorf tubes. Sample preparation was performed at microscale (115 μL sample volume) with 65% nitric acid and 30% hydrogen peroxide. According to scanning electron microscopic measurements, the organic matrix of the cell samples could be eliminated to the extent that accurate results were obtained for Cu and Fe by analyzing the same samples by TXRF and GF-AAS. Concerning the iron uptake, HT-29 cells incubated in FCS-free medium contained Fe in cca. 5-50 times higher amounts compared to cells cultured in FCS supplemented medium. Pronounced differences in the iron uptake compared to the iron supply (inorganic vs. organic chelated as well as iron(II) vs. iron(III)) were observed in the case of cell lines incubated in FCS-free medium.     

Synthesis, spectral, antimicrobial and antitumor assessment of Schiff base derived from 2-aminobenzothiazole and its transition metal complexes

N-(thiophen-2-ylmethylene)benzo[d]thiazol-2-amine Schiff base (L) derived from 2-aminobenzothiazole and 2-thiophenecarboxaldehyde was synthesized and characterized using elemental analysis, IR, mass spectra, (1)H NMR and UV-vis spectra. Its complexes with Cu(II), Fe(III), Ni(II) and Zn(II) were prepared and isolated as solid products and characterized by elemental and thermal analyses, spectral techniques as well as magnetic susceptibility. The IR spectra showed that the Schiff base under investigation behaves as bidentate ligand. The UV-vis spectra and magnetic moment data suggested octahedral geometry around Cu(II) and Fe(III) and tetrahedral geometry around Ni(II) and Zn(II). In view of the biological activity of the Schiff base and its complexes, it has been observed that the antimicrobial activity of the Schiff base increased on complexation with the metal ion. In vitro antitumor activity assayed against five human tumor cell lines furnished the significant toxicities of the Schiff base and its complexes.     

The use of Si carriers for aerosol particle collection and subsequent elemental analysis by total-reflection X-ray fluorescence spectrometry

The adoption of polished Si carriers was studied for the sensitive elemental analysis of aerosol particles using total-reflection X-ray fluorescence (TXRF) spectrometry. The surface roughness of the Si carrier measured by atomic force microscopy was found to be smaller than those of glassy carbon and quartz glass carriers, which are commonly used for TXRF analysis. The detection limits of elements for the Si carrier were superior to those for the glassy carbon and the quartz glass carriers, presumably due to its smaller surface roughness. For example, the detection limit of Sr for the Si carrier was 9 pg, which was 100 times and 3 times lower than those for the glassy carbon and the quartz glass carriers, respectively. The Si carriers could be successfully applied to the direct aerosol particle collection by impaction and the subsequent elemental analysis by TXRF. From the results of the elemental analysis of aerosol particles, the variations in the concentrations of K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn Sr and Pb with time could be clarified.     

Effects of cadmium on cation concentrations in sycamore cells (Acer pseudoplatanus L.): application of EDXRF

Knowledge of the element content of biological systems is important in enabling understanding of uptake mechanisms and physiological response to stress conditions. In this work concentrations of mineral elements in sycamore (Acer pseudoplatanus L.) cells grown in the presence of cadmium have been analysed and compared with concentrations in control cells. Energy-dispersive X-ray fluorescence (EDXRF) was used to quantify the nutrients K, Ca, Mn, Fe, Cu, and Zn present in the cells. The reproducibility and accuracy of the technique were demonstrated by analysis of biological reference materials. Exposure of sycamore cells to cadmium had induced variation in the content of some elements. Mn, Cu, Zn, and, particularly, Fe concentrations in cells exposed to Cd were higher than those found in control cells. Ca is adsorbed on the cell walls and the concentration of K is not affected by the presence of Cd.     

冠心病患者全血微量元素锌、铜、铁的分析

用原子吸收法测定５０例健康人、５２例冠心病患者全血微量元素锌、铜、铁的含量，并对５２例冠心病患者全血微量元素锌、铜、铁的含量及锌／铜比值，与其血脂总胆固醇（ＣＨ）、甘油三酯（ＴＧ）、高密度脂蛋白（ＨＤＬ）、低密度脂蛋白（ＬＤＬ）的浓度分别作线性相关分析。结果表明：（１）冠心病患者全血锌、铁、锌／铜比值均高于健康人（Ｐ＜０．０５），全血铜低于健康人（Ｐ＜０．０５）。（２）全血锌与ＨＤＬ呈负相关（Ｐ＜０．０１）、锌／铜比值与总胆固醇呈正相关（Ｐ＜０．０５），铁与ＬＤＬ呈正相关（Ｐ＜０．０１）．提示锌／铜比值增高及体内铁储存增加均可能是冠心病易患因素．     

激光电离飞行时间质谱技术用于古代瓷片中元素的检测及元素成像分析

采用自制激光电离飞行时间质谱(LI-TOF-MS)及多元素成像体系,尝试分析了古瓷片中的多种元素.对一块北宋龙泉青瓷瓷片及一块仿古青瓷瓷片样品进行了表面元素分析,所得多元素半定量分析结果表明,这两种瓷片的胎体和釉面中所含元素的种类及含量存在差异;同时对一块明代青花瓷片进行表面多元素成像分析,获得Co,Mn,Fe,Ni,Ba,Ca,Mg,Na,Al,Si,P,K,Cu,Zn和Rb的元素成像图.     

Quantitative bioimaging of trace elements in the human lens by LA-ICP-MS

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the quantitative imaging of Fe, Cu and Zn in cryostat sections of human eye lenses and for depth profiling analysis in bovine lenses. To ensure a tight temperature control throughout the experiments, a new Peltier-cooled laser ablation cell was employed. For quantification purposes, matrix-matched laboratory standards were prepared from a pool of human lenses from eye donors and spiked with standard solutions containing different concentrations of natural abundance Fe, Cu and Zn. A normalisation strategy was also carried out to correct matrix effects, lack of tissue homogeneity and/or instrumental drifts using a thin gold film deposited on the sample surface. Quantitative images of cryo-sections of human eye lenses analysed by LA-ICP-MS revealed a homogeneous distribution of Fe, Cu and Zn in the nuclear region and a slight increase in Fe concentration in the outer cell layer (i.e. lens epithelium) at the anterior pole. These results were assessed also by isotope dilution mass spectrometry, and Fe, Cu and Zn concentrations determined by ID-ICP-MS in digested samples of lenses and lens capsules.

Iron speciation in human cancer cells by K-edge total reflection X-ray fluorescence–X-ray absorption near edge structure analysis

X-ray absorption near edge structure (XANES) analysis in combination with synchrotron radiation induced total reflection X-ray fluorescence (SR-TXRF) acquisition was used to determine the oxidation state of Fe in human cancer cells and simultaneously their elemental composition by applying a simple sample preparation procedure consisting of pipetting the cell suspension onto the quartz reflectors.XANES spectra of several inorganic and organic iron compounds were recorded and compared to that of different cell lines. The XANES spectra of cells, independently from the phase of cell growth and cell type were very similar to that of ferritin, the main Fe store within the cell. The spectra obtained after CoCl₂ or NiCl₂ treatment, which could mimic a hypoxic state of cells, did not differ noticeably from that of the ferritin standard. After 5-fluorouracil administration, which could also induce an oxidative-stress in cells, the absorption edge position was shifted toward higher energies representing a higher oxidation state of Fe. Intense treatment with antimycin A, which inhibits electron transfer in the respiratory chain, resulted in minor changes in the spectrum, resembling rather the N-donor Fe-α,α′-dipyridyl complex at the oxidation energy of Fe(III), than ferritin. The incorporation of Co and Ni in the cells was followed by SR-TXRF measurements.     

小儿肾病综合征患儿血中锌,铜,铁,钙,铅的研究

为探讨小儿肾病综合征患儿血中锌,铜,铁钙,铅的变化规律,对６０例小儿肾病综合征和６０例正常儿童全血中锌,铜,铁、钙,铅含量进行了对比观察。结果表明,小儿肾病综合征患儿以上５种元素均比正常儿童降低,     

电感耦合等离子体原子发射光谱(ICP-AES)法测定高纯铝中Fe、Cu、Mg、Zn、Ti

建立了用电感耦合等离子体原子发射光谱(ICP-AES)法测定高纯铝中Fe、Cu、Mg、Zn、Ti的方法。详细讨论了基体元素和共存元素对分析元素的光谱干扰,以及盐酸用量的影响;选择了合适的分析谱线,同时得出了各元素的检出限。证明用基体匹配的方法在Fe 259.940nm、Cu 327.396nm、Mg279.079nm、Zn 213.856nm、Ti 334.941nm处可准确、可靠地测定高纯铝中含量范围在0.001%~0.01%的Fe、Cu、Mg、Zn、Ti元素。     

18种中药中微量元素铁锌锰铜的含量研究

为研究治疗黄褐斑常用中药中Fe、Zn、Cu、Mn的含量与药效的关系,测定了18种中药材中Fe、Zn、Cu、Mn含量,并用主成分分析法进行分析.结果表明,Fe含量最高,Zn、Mn次之,Cu最少;Zn和Cu的相关系数最大,且Zn与Cu比均大于1.说明补充Zn可以抑制Cu与酶结合,防治色斑.     

Multi-elemental analysis of produced water by synchrotron radiation total reflection X-ray fluorescence

The synchrotron radiation total reflection X-ray fluorescence (SRTXRF) technique was used for the analysis of heavy metals in produced water samples from oil field in Rio Grande do Norte, in order to determine potential sources of pollution. Since the inorganic components in produced water generally resembling sea water, pre-concentration procedures have been applied to increase the concentration of the analyte of interest and to minimize the salt matrix effects. This technique allows us to determine the contents of V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Hg and Pb in 20 produced water samples. The great majority of the sampling points presented low elemental concentration value. However, in some sample, the Fe, Ni, Cu, Zn and Hg concentration were higher than the established limits by the Brazilian legislation.     

兰州市城关区313名儿童血铅水平及其钙、铁、铜和锌的调查研究

为了解兰州市城关区儿童血铅水平及其钙、锌、铁、铜等微量元素分布状况,对兰州市城关区某幼儿园及同时期来我院儿保体检的正常儿童采耳用微量血无火焰原子吸收光谱法进行铅、钙、锌、铜、铁元素的测定。结果表明,本次调查儿童血铅≥10μg/dL者占93．9％,各年龄组间钙、锌、铜、铁有显著性差异。提示血铅水平与锌、钙存在相关关系。     

Determination of protein and trace elements in human milk using NAA and XFR techniques

The principal objective pursued in this study is to establish the base-line data on protein content and on the status of elemental composition in human milk from Sudanese subjects. The protein content was derived by multiplying the nitrogen content by a factor 6.25. The nitrogen was determined using a 14 MeV neutron generator. The median values for crude protein and the total dry matter found in this study were 1.23% (volume) and 104 g/l, respectively. Some minor and trace elements of biological significance namely, Cl, K, Ca, Mn, Fe, Cu, Zn, Cr, Co and Mo were determined using energy dispersive X-ray fluorescence spectrometry. The results obtained show good compatibility with the data reported by the WHO on elemental composition of human milk from different geographical regions.     

Chemometric Assessment of the Interactions Between the Metal Contents,Antioxidant Activity,Total Phenolics,and Flavonoids in Mushrooms

The elemental composition and antioxidant activity have been obtained for regional mushrooms species, wild and cultivated, from Dambovita County, Romania. A multivariate approach and data mining techniques (principal component analysis and cluster analysis, respectively) were applied in order to evaluate the correlation matrix for these parameters for both caps and stipes of mushrooms. The associations between metallic elements (i.e., Fe, Cu, Cd, Pb, Co, Ni, Zn, Mn, Cr, Na, K, Ca and Mg) correlated with antioxidant activity, total phenolics, and total flavonoids were carried out by using a full factorial linear design. The multivariate functional analysis revealed on associated accumulation of several elements in mushrooms. In the cluster analysis, the dataset was treated to appreciate the correlation between metals group (e.g., heavy metals, such as Fe, Cu, Cd, Pb, Co, Ni, Zn, Mn, Cr, and important nutritional elements, such as Na, K, Ca, and Mg). Fungal species with similar characteristics in terms of metal accumulation formed two distinctive clusters. From a point of view of the consumer, the content of Cd and especially Pb in the fruiting bodies of the analyzed mushrooms species may be considered elevated, so that mapping the risk is compulsory. Applying the chemometric tools in the sense mentioned above, as well as in helping the scientific research by optimizing the number of data points, was shown to be extremely useful.     

Determination of calcium, potassium, manganese, iron, copper and zinc levels in representative samples of two onion cultivars using total reflection X-ray fluorescence and ultrasound extraction procedure

The chemical characterization of onion cultivar samples is an important tool for the enhancement of their productivity due to the fact that chemical composition is closed related to the quality of the products. A new sample preparation procedure for elemental characterization is proposed, involving the acid extraction of the analytes from crude samples by means of an ultrasonic bath, avoiding the required digestion of samples in vegetable tissue analysis. The technique of total reflection X-ray fluorescence (TXRF) was successfully applied for the simultaneous determination of the elements Ca, K, Mn, Fe, Cu and Zn. The procedure was compared with the wet ashing and dry ashing procedures for all the elements using multivariate analysis and the Scheffé test. The technique of flame atomic absorption spectrometry (FAAS) was employed for comparison purposes and accuracy evaluation of the proposed analysis method. A good agreement between the two techniques was found when using the dry ashing and ultrasound leaching procedures. The levels of each element found for representative samples of two onion cultivars (Yellow Granex PRR 502 and 438 Granex) were also compared by the same method. Levels of K, Mn and Zn were significantly higher in the 438 Granex cultivar, while levels of Ca, Fe and Cu were significantly higher in the Yellow Granex PRR 502 cultivar.     

小儿肾病综合征患儿血中锌、铜、铁、钙、铜、铅的研究

The content of Zn,Cu,Fe,Ca and Pb in whole blood of children nephrotic syndrome(NS) of children Was Studied. Trace elements Zn,Cu,Fe Ca,Pb in the blood of sixty children suffering from NS and those of sixty health children were compared. The results show that the content of Zn,Cu,Fe,Ca,Pb in patient's blood is lower than normal content of controls. The coneent of Zn, Cu in blood positively correlated with total protein and albuim in blood.It suggested that the five trace elements closely correlatted with NS.     

脱发白发与微量元素关系研究

利用火焰原子吸收法测定了中国银行韶关节市分行４５８名职工头发中Ｃｕ，Ｆｅ，Ｚｎ，Ｃａ含量，运用统计学方法求出该人群中正常者与白发，脱发者Ｃｕ，Ｆｅ，ＺｎＣａ的特征含量，通过数据比较可看出，白发者Ｃｕ，Ｆｅ，Ｚｎ，Ｃａ的含量均低于正常组，而脱发者与正常组较接近，经相关性检验，证明了Ｃｕ，Ｆｅ，Ｚｎ，Ｃａ偏低的血发存在的相关性，与脱发没有相关性，经过性别比对，女性发中Ｃｕ，Ｆｅ，Ｚｎ，Ｃａ含量均高于男     

Direct analysis of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powders by total reflection X-ray fluorescence spectrometry

A direct analysis procedure for the determination of trace impurities of Ca, V, Cr, Mn, Fe, Ni, Cu, Zn and Ga in Al₂O₃ ceramic powders by total reflection X-ray fluorescence spectrometry (TXRF) is described. The powders were analysed in the form of slurries containing 1–10 mg mL^–1 of powder. The use of the procedure in the case of powders with differing grain size and for different slurry concentrations was investigated. Three different quantification possibilities were compared, namely the use of Al as a matrix component, the use of Fe as a trace element contained in the sample or of Co added in concentrations of 200 g g^–1 as internal standard. The homogeneity of elemental distributions in sample layers deposited on the TXRF quartz carriers by evaporating 5 L of the 10 mg mL^–1 slurries was studied by scanning the 4- to 5-mm-diameter spots of two samples by synchrotron radiation TXRF at Hasylab. For powders with differing graininess but mainly finer than about a few 10 m, no systematic influence of the grain size on the accuracy of the determinations of Ca, V, Fe, Ni, Cu and Zn could be observed. The measurement precision, however, seemed to be limited by inhomogeneous distributions of the trace elements in the samples as testified by the synchrotron radiation TXRF scans. Detection limits of the developed TXRF procedure for Ca, V, Cr, Mn, Fe, Ni, Cu, Zn and Ga were found to be in the 0.3–7 g g^–1 range and were shown to increase slightly with the grain size of the samples. Quantification using Al (matrix) as internal standard led to systematically higher values out of the accuracy required, whereas the other two approaches in all cases led to reliable results.Dedicated to the memory of Wilhelm Fresenius     

Instrumental neutron activation analysis of the hair of metallurgical workers

Hair samples were collected from 20 metallurgical workers (10 males and 10 females) and from 59 control subjects (32 males and 27 females), whose jobs do not indicate a specific occupational exposure. The concentrations of ten minor and trace elements (Al, Co, Cu, Fe, Mg, Mn, Sb, Se, V and Zn) were determined by instrumental neutron activation analysis (INAA). The statistical data distributions, the sex and age influences in these elemental concentrations and the average values obtained for the control group were compared with published data. The effect of occupational exposure to the metallic elements was reflected in elemental composition of hair by significant higher concentration levels of Al, Co, Cu, Fe, Mg, Mn, Sb, V and Zn in the hair of the exposed group, when compared with the control group.