The determination of chromium-50 in human blood and its utilization for blood volume measurements

Possible relationships between insufficient blood volume increases during pregnancy and infant mortality could be established with an adequate measurement procedure. An accurate and precise technique for blood volume measurements has been found in the isotope dilution technique using chromium-51 as a label for red blood cells. However, in a study involving pregnant women, only stable isotopes can be used for labeling. Stable chromium-50 can be determined in total blood samples before and after dilution experiments by neutron activation analysis (NAA) or mass spectrometry. However, both techniques may be affected by insufficient sensitivity and contamination problems at the inherently low natural chromium concentrations to be measured in the blood. NAA procedures involving irradiations with highly thermalized neutrons at a fluence rate of 2·10¹³ n·cm^–2·s^–1 and low background gamma spectrometry are applied to the analysis of total blood. Natural levels of chromium-50 in human and animal blood have been found to be <0.1 ng/ml; i.e., total chromium levels of <3 ng/ml. Based on the NAA procedure, a new approach to the blood volume measurement via chromium-50 isotope dilution has been developed which utilizes the ratio of the induced activities of chromium-51 to the iron-59 in three blood samples taken from each individual, namely blank, labeled and diluted labeled blood.     

苯丙酮尿症新生儿血斑中辅酶及葡萄糖等物质的分析

苯丙酮尿症(PKU)是新生儿先天性苯丙氨酸羟化酶缺陷所引起的苯丙氨酸代谢障碍疾病.本研究采用超高效液相色谱-质谱联用技术, 测定了5例PKU新生儿出生3天和出生30天后的血斑与20例年龄相仿的正常新生儿血斑中辅酶Q10的绝对含量和辅酶Q9的相对含量,其中,健康新生儿血斑中辅酶Q10的含量为(122.1±24.9) ng/mL,PKU新生儿组的含量为(59.0±12.0) ng/mL.采用气相色谱-质谱联用技术测定了胆固醇和葡萄糖的相对含量.研究结果表明,与对照组相比,PKU新生儿血斑中辅酶Q10、Q9、胆固醇和葡萄糖的含量均显著降低,辅酶Q10的降低与血斑中苯丙氨酸含量升高呈现显著反向相关.本研究结果为PKU患儿的饮食治疗方案提供了依据.     

Determination of trace amounts of cadmium, cobalt, chromium, iron, molybdenum, nickel, selenium, titanium, vanadium and zinc in blood and milk by neutron activation analysis

The concentrations of Cd, Co, Cr, Fe, Mo, Ni, Se, Ti, V and Zn in biological fluids, human blood serum and market milk were determined by neutron activation analysis, with enrichment by coprecipitation. The pre-concentration of these trace elements was accomplished by converting the dissolved trace metal ions into their pyrrolidinedithiocarbamate (1-pyrrolidinecarbodithioate) chelates, followed by coprecipitation with a metal carrier such as Ni, Pb or Bi. The coprecipitation was carried out prior to irradiation for the short-lived nuclides (V, Ti and Se) and after irradiation for the other elements. The validity of the method was checked using certified biological reference materials; the concentrations of trace elements found by the proposed method agreed well with the published certified data. The limits of detection for Cd, Co, Cr, Fe, Mo, Ni, Se (obtained through the long-lived isotope 75Se) and Zn under the present experimental conditions were found to be 5, 5, 10, 520, 5, 70, 10 and 150 ng, respectively, for 5 ml of biological liquor. The limits of detection for Ti and V obtained (through their short-lived radionuclides 51Ti and 52V, respectively) were found to be 180 and 1.4 ng, respectively, for 50 ml of market milk, or 70 and 0.7 ng for 1 ml of blood serum.     

Multi-element analysis of blood for trace metals by neutron activation analysis

Fourteen elements can be rapidly determined in whole blood by the neutron activation analysis procedure described. Three of these (Ag, Cl, Se) are measured after a 10-s irradiation and eleven others (Al, Ba, Br, Ca, Cu, I, Mg, Mn, Mo, Rb, V) are determined by a 180-s irradiation of a 1-cm³ sample of whole blood after destruction of organic matter and removal of sodium by hydrated antimony pentoxide. A further 13 elements (As, Au, Co, Cr, Cs, Fe, Hg, K, Na, Ni, Sb, Sc, Zn) are determined after overnight irradiation in the SLOWPOKE reactor.     

Critical evaluation and experimental determination of the nuclear activation and decay parameters for the reactions:50Cr(n, ψ)51Cr,58Fe(n, ψ)59Fe,109Ag(n, ψ)110mAg

Isotopic abundance values for⁵⁰Cr,⁵⁸Fe and¹⁰⁹Ag and the absolute gamma-intensities for⁵¹Cr,⁵⁹Fe and^110mAg were evaluated. These evaluated data, together with experimental k₀-determinations (i.e. from the “activation method”), made it possible to calculate the following 2200 m.s^?1 cross-sections, which considerably deviate from the hitherto generally published ones [between brackets]: $$\begin{gathered} {}^{5 0}Cr(n,\gamma )^{5 1} Cr; \sigma _0 = (15.2 \pm 0.2) barn [cf.:15.8 - 16.0] \hfill \\ {}^{5 8}Fe(n,\gamma )^{5 9} Fe; \sigma _0 = (1.31 \pm 0.03) barn [cf.:1.14 - 1.16] \hfill \\ {}^{1 0 9}Ag(n,\gamma )^{1 1 0 m} Ag;\sigma _0 = (3.89 \pm 0.05) barn [cf.:4.4 - 5.0] \hfill \\ \end{gathered} $$      

基于错流过滤原理的微流控细胞分离芯片的研制

首次提出并制备了一种错流过滤式细胞分离微流控芯片.     

Activation analysis of Co-60 encapsulated in stainless steel needles

Summary Cobalt-60 clinical sources have wide applications in cancer treatment. Non-destructive activation analysis has been employed to assess the radiometric purity of cobalt needles encapsulated in stainless steel sheet after pile irradiation.The main radio impurities detected in these needles are⁵⁴Mn,⁵⁹Fe and⁵¹Cr. Although the activity of the impurities represented 21% of the total activity within 15 days after irradiation, the purity of needles improves fastly to about 99% after 7 months. Moreover, increasing the amount of irradiated cobalt would result in high specific activity needles with the same radiometric purity within a reduced cooling period.

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Zusammenfassung In der klinischen Krebsbekämpfung findet⁶⁰Co als Strahlenquelle verbreitete Anwendung. Die radiometrische Reinheit von Kobaltnadeln, die nach der Bestrahlung in einem Behälter aus rostfreiem Stahl verschlossen waren, wurde im Wege einer zerstörungsfreien Aktivierungsanalyse bestimmt. Die wichtigsten radioaktiven Verunreinigungen in diesen Nadeln waren⁵⁴Mn,⁵⁹Fe und⁵¹Cr. Obwohl die Aktivität dieser Verunreinigungen 21% der Gesamtaktivität innerhalb von 15 Tagen nach der Bestrahlung betrug, verbessert sich die Reinheit der Nadeln rasch auf etwa 99% nach 7 Monaten. Überdies würden steigende Mengen bestrahlten Kobalts Nadeln hochspezifischer Aktivität mit gleicher radiometrischer Reinheit in einer kürzeren Abklingperiode ergeben.

     

Comparison of heavy metal analyses in hydrofluoric acid used in microelectronic industry by ICP-MS and thermal ionization isotope dilution mass spectrometry

An isotope dilution mass spectrometric (IDMS) method with the thermal ionization (TI) technique has been developed for the determination of trace impurities of Cr, Fe, Ni, Cu, Zn, Ag, Cd, Tl, Pb, Th, and U in high-purity HF (50% by weight) used in the semiconductor industry. The evaporation step of the HF solution was carried out in an apparatus which did not significantly contribute to contaminations of the heavy metals to be analysed. This apparatus allowed fast evaporation of the HF solution of up to 200 ml/h and therefore also a fast trace heavy metal/matrix separation was carried out. The evaporation step was also used in connection with inductively coupled plasma mass spectrometry (ICP-MS) when applying the isotope dilution technique and an external calibration for quantification, respectively. The detection limits for TI-IDMS were (in pg/g): Cr=30, Fe=400, Ni=70, Cu=20, Zn=1100, Ag=70, Cd=10, Tl=1, Pb=16, Th=3, and U=1. With ICP-MS in combination with the evaporation step, detection limits of less than 50 pg/g have been achieved for Cr, Ni, and Zn and of <5 pg/g for the other elements except Fe, which could not be determined in concentrations less than 100 ng/g. On the other hand, the detection limits were much higher when the HF matrix was not removed before measuring by ICP-MS. A comparison of the different ICP-MS methods (isotope dilution technique and external calibration for both HF evaporated samples and those with HF matrix) with the results of TI-IDMS has been carried out. An excellent agreement was achieved between the results of TI-IDMS and the two ICP-MS methods using the HF evaporation step, whereas the ICP-MS techniques without HF evaporation essentially deviated from these results. Fe was the only trace element of all investigated heavy metals which could only be analysed by TI-IDMS in high purity HF in a concentration of about 3 ng/g. Although ICP-MS with isotope dilution and external calibration resulted in comparable analytical data, the ICP-IDMS method has some practical advantages such as time-saving and more reliable results.     

Interface characteristics in diffusion bonding of Fe3Al with Cr18-Ni8 stainless steel

Fe3Al and Cr18-Ni8 stainless steel were diffusion-bonded in vacuum and a Fe3Al/Cr18-Ni8 interface with reaction layer was formed. Microstructure in the reaction layer at Fe3Al/Cr18-Ni8 interface was analyzed by means of scanning electron microscope (SEM) and electron probe micro-analyzer (EPMA). The growth of reaction layer with heating temperature (T) and holding time (t) was researched. The results indicate that FeAl, Fe3Al, Ni3Al, and alpha-Fe (Al) solid solution are formed in the reaction layer. These phases are favorable to promote the element diffusion and to accelerate the formation of the reaction layer at Fe3Al/Cr18-Ni8 interface. The growth of reaction layer obeys the parabolic law and its thickness (X) is expressed by X2 = 7.5 x 10(-4)exp(-83.59/RT)(t - t0).     

Instant capture of recoil51Cr(III) from neutron activated K2CrO4

We have recently developed a new method of measuring the initial⁵¹Cr(III) produced from nuclear recoil of K₂CrO₄. In our method, K₂CrO₄ was mixed with MgO in the presence of a small amount of water, and the mixture was irradiated in a nuclear reactor. After irradiation, the mixture was dissolved in water, and MgO precipitate was separated from the solution. The yield of recoil⁵¹Cr(III) could be calculated from the⁵¹Cr activity in the precipitate measured. On the other hand, the yield of retention of⁵¹Cr as chromate could be calcualted from the activity found in the supernatant. The⁵¹Cr(III) yield thus obtained is almost a factor of 2 higher than observed in pure K₂CrO₄ without mixing with MgO, irradiated under the same condition. Another important observation is that the⁵¹Cr(III) yield is independent of irradiation time in the presence of MgO. Without MgO, the observed⁵¹Cr(III) yield decreases with increasing irradiation time, suggesting possible oxidation of Cr(III) to chromate during irradiation. This variation is not observed in the system of K₂CrO₄ containing MgO, indicating that the initial Cr(III) is adsorbed immediately after nuclear recoil by MgO and is protected from oxidation by gamma radiation.     

Neutron energy spectrum determination and flux measurement using MAXED, GRAVEL, and MCNP for RACE experiments

Stainless steel flux wires were used to determine the neutron energy spectra and total flux during the Reactor Accelerator Coupling Experiments (RACE) at The University of Texas at Austin. A LINAC electron accelerator produced 20 MeV electrons at a power of 1.6 kW, which struck a tungsten-copper target to produce bremsstrahlung radiation and photoneutrons. The neutrons produced in the target were multiplied by the subcritical core of a Triga reactor. The purpose of the RACE experiments is to develop a sub-critical accelerator driven system that would be capable of transmuting actinides from spent fuel. Flux measurements were made with 1.58 mm diameter stainless steel wires placed throughout the core between the fuel rods and cadmium covered and uncovered gold and indium foils above the target. The MAXED and GRAVEL computer codes were used to perform the spectrum unfolding. The composition of the stainless steel wires was determined using neutron activation analysis with comparators prior to the flux measurement. The reactions measured in the stainless steel to determine the flux were ⁵⁰Cr(n,γ)⁵¹Cr, ⁵⁸Ni(n,p)⁵⁸Co, ⁵⁴Fe(n,p)⁵⁴Mn, and ⁵⁸Fe(n,γ)⁵⁹Fe. Flux measurements agreed well with an MCNP simulation of the experiment.     

Blood volume and red cell mass in children with moderate and severe malaria measured by chromium‐53 dilution and gas chromatography/mass spectrometric analysis

Understanding blood volume changes in children with malaria is important for managing fluid status. Traditionally, blood/red cell volume measurements have used radioactive chromium isotopes. We applied an alternative approach, using non‐radioactive chromium‐53 labelling and mass spectrometry to investigate red cell volume (RCV) in Gabonese children with malaria. Nineteen children with malaria participated (10 severe, 9 moderately severe; ages 15 months to 7 years). Blood labelled with ⁵³Cr‐chromate ex vivo was re‐injected, then sampled 30 min later. Pre‐ and post‐injection ⁵³Cr content were measured by gas chromatography/electron ionisation mass spectrometry of the chromium‐trifluoroacetylacetone (TFA) chelate, calibrated against ⁵⁰Cr standards. Blood and red cell volumes were calculated from isotopic dilution in 15 of 19 children (in four, insufficient signal mitigated analysis). In this small pilot study, there were no significant differences between moderate and severe cases. Including all subjects, the mean RCV was reduced compared with predicted values (184 vs. 269 mL; p = 0.016) but blood volume, 71 ± 33 mL/kg (normalised for weight), was close to predicted, ～77 mL/kg, commensurate with reduced haematocrit. Blood lactate concentration correlated negatively with RCV/weight (r = ?0.56, p = 0.028), consistent with anaemia. In one case, sequential samples over 42 days gave an estimated rate of ⁵³Cr disappearance of 1.4%/day (equivalent half‐life: 70 days). ⁵³Cr‐labelling of red cells may be used to estimate blood and red cell volumes and can be used as an investigative tool in situations such as childhood diseases and resource‐constrained settings. Although the red cell mass is depleted in malaria, the blood volume appears relatively well preserved. Copyright © 2009 John Wiley & Sons, Ltd.     

Aktivierungsanalytische Bestimmung von metallischen Verunreinigungen in KNK-Prim?rnatrium

Zusammenfassung Durch Bestrahlung im FR2 wurden in neun Proben des KNK-Primärnatriums aktivierungsanalytisch Fe, Cr, Co, Sb, Zn, Ag und Hg bestimmt. Zn (3.7 ppm), Ag (0.1 ppm) und Hg 0.02 ppm) waren recht gleichmäßig verteilt, während die Werte für Fe, Cr, Co und Sb von Probe zu Probe stark schwankten.Aus den Mittelwerten der Metallgehalte in den neun bestrahlten Proben wurden die Aktivitäten der Nuklide Cr-51, Fe-59, Co-60, Zn-65, Ag-110m, Sb-122, Sb-124 und Hg-203 errechnet, die im Primärnatrium nach 100 bzw. 200 Tagen Vollastbetrieb vorliegen werden. Die spezifische Aktivität des Na-22 wird in der KNK-I nach weniger als einem Monat Betrieb ihren Sättigungswert von etwa 50 nCi/g Na erreicht haben.Der Kernkraftwerk-Betriebsgesellschaft mbH (KBG) danken wir für das Überlassen der Natriumproben, Herrn W. Rottmann für die Durchführung der Neutronenfluß-Messungen.     

Stable-isotope dilution analysis of galactose metabolites in human erythrocytes

An established gas chromatography/mass spectrometry (GC/MS) method, devised for stable-isotope dilution analysis of plasma galactose, was developed to allow determination of erythrocyte (red blood cell, RBC) concentrations of galactose-1-phosphate and other primary metabolites relevant in galactosaemia. Galactose-1-phosphate was enzymatically converted to galactose, and the aldononitrile pentaacetate derivative was separated by gas chromatography and determined by mass spectrometry using chemical ionisation and selected ion monitoring of the [MH-60](+) ion. U-(13)C-Labelled standard was used for quantification. Comparative measurements were conducted using established fluorimetric and radiometric enzymatic methods. The GC/MS analysis for galactose-1-phosphate was linear (range examined 0-600 micromol/L(RBC), packed cells), of acceptable repeatability at low and high concentrations (within and between run CVs <15%), with a limit of quantification of 0.01 micromol/L(RBC). With samples from patients with classical galactosaemia there was a linear correlation with conventional enzymatic assays (r(2) > 0.927). In erythrocytes from post-absorptive patients under treatment, Q188R-heterozygous parents, and healthy subjects, galactose-1-phosphate concentrations (mean +/- SD) were found to be 142 +/- 38 (n = 41), 1.4 +/- 0.2 (n = 8), and 1.9 +/- 0.5 (n = 33) micromol/L(RBC), respectively. In comparison, free galactose concentrations were 3.8 +/- 1.7, 0.49 +/- 0.19, and 0.43 +/- 0.20 mol/L(RBC), respectively. The procedure allowed simultaneous galactitol analysis and proved to be useful to trace incorporation of (13)C-label into erythrocyte galactose metabolites in a D-[1-(13)C]galactose in vivo turnover study.     

Spectroscopic approach in characterization of chromium(III), manganese(II), iron(III) and copper(II) complexes with a nitrogen donor tetradentate, 14-membered azamacrocyclic ligand

The complexes of Cr(III), Mn(II), Fe(III) and Cu(II) were synthesized with the macrocyclic ligand i.e. 2,3,9,10-tetraketo-1,4,8,11-tetraazacyclotetradecane. The ligand was prepared by the [2 + 2] condensation reaction of diethyloxalate and 1,3-diamino propane. These complexes were found to have the general composition M(L)X3 and M'(L)X2 [where M = Mn(II) and Cu(II), M' = Cr(III) and Fe(III), L = ligand (N4) and X = Cl-, NO3-, 1/2SO4(2-) and [CH3COO-]. The ligand and its transition metal complexes were characterized by the elemental analyses, molar conductance, magnetic susceptibility, mass, IR, electronic, and EPR spectral studies. On the basis of IR, electronic and EPR spectral studies an octahedral geometry has been assigned for Cr(III), Mn(II) and Fe(III) and a tetragonal geometry for Cu(II) complexes.     

Use of Escherichia coli immobilized on amberlite XAD-4 as a solid-phase extractor for metal preconcentration and determination by atomic absorption spectrometry.

A sensitive solid-phase extraction technique (SPE) for the enrichment of Fe(III), Co(II), Mn(II) and Cr(III) prior to atomic absorption spectrometric analysis is described. Escherichia coli immobilized on Amberlite XAD-4 was used as a solid-phase extractor. The effects of the pH, amount of solid-phase, eluent type and volume of the sample solution on the recovery of the metal ions were investigated. The effect of diverse ions was also investigated. The recoveries of Fe(III), Co(II), Mn(II) and Cr(III) under the optimum conditions were found to be 99 +/- 2, 99 +/- 3, 98 +/- 2, 98 +/- 3%, respectively, at the 95% confidence level. The detection limits of the metal ions were found as to be 2.4, 3.8, 1.3 and 1.7 ng ml(-1) for Fe(II), Co(II), Mn(II) and Cr(III) respectively, by applying a preconcentration factor of 25. The proposed enrichment method was applied to the determination of analytes in Atatürk Dam water samples, and alloy samples (RSD < 5%). The accuracy of the method was verified on certified alloy samples (NBS SRM 85b and NBS SRM 59a). The analytes were determined with a relative error lower than 5% in water and alloy samples.     

13X分子筛负载Fe催化剂上1,4-二氧六环在空气中完全氧化(英文)

采用浸渍法制备了不同Fe含量的13X分子筛负载的Fe催化剂(Fe/X13),运用N_2吸附-脱附法测得其BET比表面积和BJH孔径分布,采用X射线衍射、扫描电镜、程序升温还原和NH_3程序升温脱附法表征了该催化剂的织构性质.在固定床流动反应器中,以空气为氧化剂、在100-400℃范围内考察了Fe/X13催化剂上1,4-二氧六环的完全氧化反应性能,研究了反应温度、金属担载量和气体空速(GHSV)等条件对催化氧化降解二氧六环反应性能的影响,并在400℃测定了该催化剂反应50h的稳定性,结果表明,6 wt%Fe/13X催化剂表现出最高的催化性能,在400℃,GHSV=24000 h~(-1)的条件下,二氧六环转化率为97%,生成CO和CO_2的选择性达95%,降解产物还包括少量的乙醛、乙二醇-甲酸酯、乙二醇二甲酸、1,4-二氧六环-2醇、1,4-二氧六环-2酮及2-甲氧基1,3二氧戊环.基于这些经色谱-质谱联用仪检测出的产物,提出了可能的1,4-二氧六环降解机理。     

Characterization of the neutron flux gradients in typical irradiation channels of a TRIGA Mark II reactor

The neutron distribution in a defined volume (gradient) for different matrices (air, water, cellulose, biological material and silicon dioxide) in two typical irradiation channels (pneumatic tube (PT) and IC40-channel in the carousel facility) in the TRIGA Mark II reactor at the Joef Stefan Institute (IJS) was studied. Our experiment was based on inserting Fe wires (flux monitors) into the chosen matrices. The wires were cut into small pieces after irradiation and the induced activities of ⁵⁹Fe measured. The results showed that for the studied geometry the average spatial thermal neutron flux inhomogeneities (for five studied matrices) are about 2.3% in the PT-channel and about 2.9% in the IC40-channel.     

Laser-photophoretic migration and fractionation of human blood cells

Laser photophoretic migration behavior of human blood cells in saline solution was investigated under the irradiation of Nd:YAG laser beam (532 nm) in the absence and the presence of the flow in a fused silica capillary. Red blood cells (RBC) were migrated faster than white blood cells (WBC) and blood pellets to the direction of propagation of laser light. The observed photophoretic velocity of RBC was about 11 times faster than those of others. This was understood from the larger photophoretic efficiency of RBC than that of WBC, which was simulated based on the Mie scattering theory. Furthermore, it was found that, during the photophoretic migration, RBCs spontaneously orientated parallel to the migration direction so as to reduce the drag force. Finally, it was demonstrated that RBC and WBC were separated in a micro-channel flow system by the laser photophoresis.     

Analysis of polyfluoroalkyl substances and bisphenol A in dried blood spots by liquid chromatography tandem mass spectrometry

Dried blood spots (DBS), collected as part of the newborn screening program (NSP) in the USA, is a valuable resource for studies on environmental chemical exposures and associated health outcomes in newborns. Nevertheless, determination of concentrations of environmental chemicals in DBS requires assays with great sensitivity, as the typical volume of blood available on a DBS with 16-mm diameter disc is approximately 50 μL. In this study, we developed a liquid–liquid extraction and high-performance liquid chromatography/tandem mass spectrometry method for the detection of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and bisphenol A (BPA) in DBS. The method was validated for accuracy, precision, and sensitivity, by spiking of target chemicals at different levels on Whatman 903 filter cards, which is used in the collection of DBS by the NSP. Contamination arising from collection, storage, and handling of DBS is an important issue to be considered in the analysis of trace levels of environmental chemicals in DBS. For the evaluation of the magnitude of background contamination, field blanks were prepared from unspotted portions of DBS filter cards collected by the NSP. The method was applied for the measurement of PFOS, PFOA, and BPA in 192 DBS specimens provided by NSP of New York State. PFOS and PFOA were detected in 100 % of the specimens analyzed. The concentrations of PFOS and PFOA measured in DBS were similar to those reported earlier in the whole blood samples of newborns. BPA was also found in 86 % of the specimens at concentrations ranging from 0.2 to 36 ng/mL (excluding two outliers). Further studies are needed to evaluate the sources of BPA exposures and health outcomes in newborns.