Radiochemical separation of 224Ra from 232U and 228Th sources for 224Ra/212Pb/212Bi generator.

The application of diagnostic and therapeutic radionuclides in nuclear medicine has grown significantly and has translated into the increased interest in radionuclide generators and their development. 224Ra and its shorter-lived daughters, 212Pb and 212Bi, are very interesting radionuclides from Targeted Alpha Therapy point of view for treatment of small cancers or metastatic forms. The purpose of the present work was to develop a simple generator for rapid elution of carrier-free 224Ra from 232U or 228Th sources by radiochemical separation based on extraction chromatography with the utilization of a home-made material. The bis(2-ethylhexyl) hydrogen phosphate (HDEHP) extractant was immobilized on polytetrafluroethylene (PTFE) grains and its ability to selectively adsorb 232U and 228Th, with simultaneous high elution recovery of 224Ra, was checked over few years. The 224Ra was quantitatively eluted with small volume (3-5 mL) of 0.1 M HNO3 with low breakthrough (<0.005%) and was used for further milking of 212Bi and 212Pb from DOWEX 50WX12 by 0.75 M and 2.0 M HCl, respectively. The elaborated here methods allowed high recovery of 224Ra, 212Pb and 212Bi radionuclides and their application in radiolabeling of various biomolecules.

Magnetically separable BiOBr/Fe3O4@SiO2 for visible-light-driven photocatalytic degradation of ibuprofen: Mechanistic investigation and prototype development.

The increasingly ubiquitous release of emerging refractory pollutants into water is a serious concern due to associated risks. In this study, mesoporous hierarchical BiOBr/Fe3O4@SiO2-a solvothermally synthesized visible-light-driven magnetic photocatalyst-not only exhibited fast kinetics (t1/2 = 8.7 min) in the photocatalytic degradation of ibuprofen in water but also achieved almost complete mineralization over a prolonged irradiation of 6 h. Various reactive species, including O2¯, OH, and H2O2, were detected, while the scavenging experiments revealed that eCB--mediated reactions and direct-hole oxidation are the major degradation routes. The magnetically recycled BiOBr/Fe3O4@SiO2 maintained ∼80% of its initial photocatalytic activity even after five consecutive cycles. The typically copresent wastewater constituents, including NOM and anions, inhibited the photocatalytic performance to varying extents, and hence necessitated an increase in the photocatalyst dosage to achieve complete ibuprofen degradation in real sewage. Based on the findings of batch experiments, the process was scaled up by developing a 5 L prototype photocatalytic reactor integrated with an electromagnetic separation unit. The results of prototype photocatalytic experiments were comparable to those of batch experiments, and an electromagnetic separation efficiency of ∼99% was achievable in 5 min.

Facile Chip-Based Array Monolithic Microextraction System Online Coupled with ICPMS for Fast Analysis of Trace Heavy Metals in Biological Samples.

Trace heavy metals have great impact on biological system; therefore, it is essential to develop suitable analytical methods for the determination of trace heavy metals in biological samples to elucidate their biochemical and physiological functions in organisms. Herein, we presented a chip-based array monolithic microextraction system and combined it with inductively coupled plasma mass spectrometry (ICPMS) for online analysis of trace Hg, Pb, and Bi in real-world biological samples. Six ethylenediamine modified poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) (poly(GMA-co-EDMA-NH2)) capillary monolithic columns were embedded parallelly in microchannels of a microfluidic chip for array monolithic microextraction. Various parameters affecting the chip-based array monolithic microextraction of target metals were investigated. The sample throughput of the proposed method was 16 h-1, with the limits of detection for Hg, Pb, and Bi of 23, 12, and 13 ng L-1, respectively. The developed method was validated by the determination of trace Hg, Pb, and Bi in HepG2 cells and human urine samples, and the recoveries for the spiked samples were in the range of 90.4-102%. This chip-based array monolithic microextraction system is easy to prepare, and the proposed online analytical system provides a new platform for trace elements analysis in biological samples with the merits of high sample throughput, high sensitivity, and low sample/reagents consumption.

A new supramolecular based liquid solid microextraction method for preconcentration and determination of trace bismuth in human blood serum and hair samples by electrothermal atomic absorption spectrometry.

A simple and reliable supramolecule-aggregated liquid solid microextraction method is described for preconcentration and determination of trace amounts of bismuth in water as well as human blood serum and hair samples. Catanionic microstructures of cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) surfactants, dissolved in deionized water/propanol, are used as a green solvent to extract bismuth (III)-diethyldithiocarbamate complexes by dispersive microextraction methodology. The extracted solid phase is easily removed and dissolved in 50 µL propanol for subsequent measurement by electrothermal atomic absorption spectrometry (ET-AAS). The procedure benefits the merits of supramolecule aggregates' properties and dispersive microextraction technique using water as the main component of disperser solvent, leading to direct interaction with analyte. Phase separation behavior of extraction solvent and different parameters influencing the extraction efficiency of bismuth ion such as salt concentration, pH, centrifugation time, amount of chelating agent, SDS:CTAB mole ratio, and solvent amounts were thoroughly optimized. Under the optimal experimental conditions, the calibration curve was linear in the range of 0.3-6 µg L-1 Bi (III) with a limit of detection (LOD) of 0.16 µg L-1 (S/N = 3). The relative standard deviations (RSD) of determination were obtained to be 5.1 and 6.2 % for 1 and 3 µg L-1 of Bi (III), respectively. The developed method was successfully applied as a sensitive and accurate technique for determination of bismuth ion in human blood serum, hair samples, and a certified reference material.

Analytical method for the determination of trace toxic elements in milk based on combining Fe3O4 nanoparticles accelerated UV fenton-like digestion and solid phase extraction.

A UV Fenton-like digestion method was developed first time for a complete digestion of milk samples by using 1.6 g L(-1) Fe3O4 magnetic nanoparticles, 0.2% (v/v) nitric acid, and 6% (w/w) H2O2. During the digestion, the liberated As-, Sb-, and Bi-containing species were preconcentrated onto the surface of Fe3O4 magnetic nanoparticles, which were conveniently separated with a hand-held magnet and subsequently dissolved in hydrochloric acid prior to hydride generation atomic fluorescence spectrometric detection. Owing to the integration of UV Fenton-like digestion, solid phase extraction, and magnetic separation into a single step, the developed method significantly simplifies sample preparation steps and reduces chemical consumption and hazardous waste. Limits of detection of 0.0015, 0.0022, and 0.0025 µg L(-1) were obtained for As, Sb, and Bi, respectively, using a 50 mL milk sample. The method was applied to the determination of these elements in a Certified Reference Material and milk samples.

Preparation, characterization, and anti-Helicobacter pylori activity of Bi3+-Hericium erinaceus polysaccharide complex.

Two new Bi3+-Hericium erinaceus polysaccharide (BiHEP) complexes were prepared using Bi3+ and two purified polysaccharides from H. erinaceus (HEPs), respectively. The complexes were characterized by elemental analysis, FT-IR, CD, SEM, AFM, XRD, and TG. The anti-Helicobacter pylori (Hp) activities in vitro by agar dilution assay of the complexes were evaluated. The molecular weights of HEPs were 197 and 20 kDa, respectively. All the analyses confirmed the formation of new BiHEP complexes with lower content of Bi3+ compared with colloidal bismuth subcitrate (CBS), the most utilized bismuth preparation clinically. Furthermore, HEPs themselves have definite inhibition effects on Hp, and BiHEP complexes have lower content of Bi exhibited strong inhibition effects on Hp (MIC=20 µg/mL), similar to that of CBS with higher content of Bi. The study provides a basis for further development of multiple treatments of Hp infection or new medicines.

Large-scale synthesis of bismuth hollow nanospheres for highly efficient Cr(VI) removal.

Bismuth hollow nanospheres were successfully synthesized via a facile solvothermal method and exhibit highly efficient Cr(VI) removal capacities in a wide pH range (2-11).

Bismuth-213 and actinium-225 -- generator performance and evolving therapeutic applications of two generator-derived alpha-emitting radioisotopes.

The alpha emitters (225)Ac and (213)Bi are promising therapeutic radionuclides for application in targeted alpha therapy of cancer and infectious diseases. Both alpha emitters are available with high specific activity from established radionuclide generators. Their favourable chemical and physical properties have led to the conduction of a large number of preclinical studies and several clinical trials, demonstrating the feasibility, safety and therapeutic efficacy of targeted alpha therapy with (225)Ac and (213)Bi. This review describes methods for the production of (225)Ac and (213)Bi and gives an overview of (225)Ac/(213)Bi radionuclide generator systems. Selected preclinical studies are highlighted and the current clinical experience with (225)Ac and (213)Bi is summarized.

Investigation of novel rapidly synergistic cloud point extraction pattern for bismuth in water and geological samples coupling with flame atomic absorption spectrometry determination.

Rapidly synergistic cloud point extraction (RS-CPE) greatly simplified and accelerated the procedure of traditional cloud point extraction (CPE). In order to expand the application of RS-CPE, this work was carried out after the establishment of the improved extraction technique. The new established extraction method was firstly applied for bismuth extraction and determination coupled with flame atomic absorption spectrometry (FAAS) in this work. The improved RS-CPE was accomplished in the room temperature in 1 min. Non-ionic surfactant Triton X-100 (TX-100) was used as extractant. Octanol worked as cloud point revulsant and synergic reagent. TX-100 has a relatively high cloud point temperature (CPT), which limited its application in CPE. In this work, TX-100 accomplished the RS-CPE procedure in room temperature successfully. The factors influencing RS-CPE, such as concentrations of reagents, pH, conditions of phase separation, effect of environmental temperatures, salt effect and instrumental conditions, were studied systematically. Under the optimal conditions, the limit of detection (LOD) for bismuth was 4.0 µg L(-1), with sensitivity enhancement factor (EF) of 43. The proposed method greatly improved the sensitivity of FAAS for the determination of bismuth and was applied to the determination of trace bismuth in real and certified samples with satisfactory analytical results. The proposed method was rapid, simple, and sensitive.

[Bamboo carbon as sorbent for the separation and preconcentration of bismuth with detection by HG-AFS and ICP-MS].

A procedure for the separation and preconcentration of bismuth was developed in a sequential injection system by employing bamboo carbon as sorbent. The detection was facilitated by both hydride generation atomic fluorescence spectrometry and inductively coupled plasma mass spectrometry. With a sample volume of 1 mL, a detection limit of 13 ng x L(-1) was obtained, along with a precision of 0.9% (0.3 microg x L(-1), n = 9) with detection by HG-AFS, and a detection limit of 10 ng x L(-1) along with a precision of 2.8% (0.3 microg x L(-1), n = 5) was achieved with detection by ICP-MS. The present system was validated by analyzing a certified reference material of river sediment (CRM 320), and spiking recovery of bismuth in human whole blood was performed with hydride generation atomic fluorescence spectrometry. No significant difference was identified in the results of bismuth detection in blood samples by hyphenating the present solid phase extraction system with detection by hydride generation atomic fluorescence spectrometry and inductively coupled plasma mass spectrometry.

Combined cation-exchange and extraction chromatographic method of preconcentration and concomitant separation of bismuth(III) with high molecular mass liquid cation exchanger.

A selective method has been developed for the extraction chromatographic separation of Bi(III) with Versatic 10 coated on silanized silica gel (SSG). Bi(III) has been quantitatively extracted from 0.1 M acetate buffer at the range of pH 5.0-5.5. The result showed that the solution pH, influent volume, flow-rate and solution temperature would affect the sorption of Bi(III). The sorbed Bi(III) was eluted with 0.1 M H(2)SO(4). The extractor system has got good values of exchange capacity (1.42 meq. of H(+) g(-1) of dry exchanger at 25 degrees C), break-through capacity (19.75 mg g(-1) at pH 5.5) and column efficiencies (300) with respect to Bi(III). The positive value of DeltaH (12.63 kJ mol(-1)) and DeltaS (0.271 kJ mol(-1) K(-1)) and negative value of DeltaG (-68.241 kJ mol(-1)) indicated that the sorption process was endothermic, entropy gaining and spontaneous in nature. P.F. has been optimized at 76.4+/-0.3 and the desorption constants K(desorption) (8x10(-3)) and K'(desorption) (1.4x10(-1)) have been determined. R(f) values and selectivity factors for diverse metal ions with respect to that of Bi(III) have been determined by ion-exchange paper chromatography. Bi(III) has been separated from synthetic mixtures containing its congeners and other metal ions associated with it in ores and alloy samples. The method was found effective for removal of Bi(III) from different water samples. A plausible mechanism for the extraction of Bi(III) has been suggested.

Headspace trapping of the hydrides on a Pd(II)-coated graphite adsorptive bar as a microextraction method for ETV-ICP-MS determination of Se, Te and Bi in seawater and human hair samples.

A new, simple and sensitive method by combining headspace Pd(II)-coated graphite bar microextraction (GBME) with electrothermal vaporization-inductively coupled plasma mass spectrometry (ETV-ICP-MS) was developed for the determination of trace Se, Te and Bi in seawater and human hair. In this method, the graphite bar was coated with Pd(II) and then used for headspace trapping of the hydrides of Se(IV), Te(IV) and Bi(III). The graphite bar with enriched hydrides of analytes was inserted directly into the graphite tube and subsequently determined by ETV-ICP-MS according to the established temperature program. The experimental parameters, which may affect the extraction and vaporization of target analytes, were systematically investigated and the optimal experimental conditions were established. Under the optimal conditions, the detection limits of the method were 8.6, 2.6 and 0.2 ng l(-1) and the relative standard deviations (RSDs) were 7.0%, 6.2% and 8.0% (C=0.20 microg l(-1), n=7) for Se, Te and Bi, respectively. Linearity was obtained over the range of 0.05-20.00, 0.01-5.00 and 0.01-20.00 microg l(-1) with the correlation coefficients of 0.9942, 0.9997 and 0.9976 for Se, Te and Bi, respectively. The proposed method was successfully applied for the determination of trace Se, Te and Bi in seawater and human hair samples. In order to validate the method, the proposed method has also been applied for the determination of trace Se, Te and Bi in the certified material of GBW07601 human hair, and the determined values were in good agreement with the certified values.

An on-line preconcentration/separation system for the determination of bismuth in environmental samples by FAAS.

An on-line preconcentration procedure for the determination of bismuth by flame atomic absorption spectrometry (FAAS) has been described. Lewatit TP-207 chelating resin, including iminodiacetate group, packed in a minicolumn was used as adsorbent material. Bi(III) was sorbed on the chelating resin, from which it could be eluted with 3 mol L(-1) HNO(3) and then introduced directly to the nebulizer-burner system of FAAS. Best preconcentration conditions were established by testing different resin quantities, acidity of sample, types of eluent, sample and eluent solution volumes, adsorption and elution flow rates, and effect of interfering ions. The detection limit of the method was 2.75 microg L(-1) while the relative standard deviation was 3.0% for 0.4 microg mL(-1) Bi(III) concentration. The developed method has been applied successfully to the determination of bismuth in pharmaceutical cream, standard reference materials and various natural water samples with satisfactory results.

Flow injection-hydride generation atomic absorption spectrometric determination of selenium, arsenic and bismuth.

A simple and robust flow injection system which permits low sample and reagent consumption is described for rapid and reliable hydride generation atomic absorption spectrometric determination of selenium, arsenic and bismuth. The system, which composed of one peristaltic pump and one four channel solenoid valve, used water as the carrier streams for both sample and NaBH(4) solution. Rapid off-line pre-reduction of the analytes was achieved by using hydroxylamine hydrochloride for selenium and a mixture of potassium iodide and ascorbic acid for arsenic and bismuth. Transition metal interference was eliminated with the addition of thiourea and EDTA into the NaBH(4) solution and significant sensitivity enhancement was observed for selenium in the presence of thiourea in the reductant solution. Under optimised conditions, the method achieved detection limits of 0.2 ng mL(-1) for Se, 0.5 ng mL(-1) for As and 0.3 ng mL(-1) for Bi. The method was very reproducible, achieving relative standard deviations of 6.3% for Se, 3.6% for As and 4.7% for Bi, and has a sample throughput of 360 h(-1). Successful application of the method to the quantification of selenium, arsenic and bismuth in a certified reference river sediment sample is reported.

[Determination of trace bismuth in traditional Chinese medicines by hydride generation atomic fluorescence spectrometry].

A method is reported for the determination of trace bismuth in traditional chinese medicine by hydride generation atomic fluorescence spectrometry. The effect of different means of digestion, the medium amounts of acid and reducing agent on the determination of Bi is investigated. In the given conditions, the linear range of determination is 0.1-200 microg x L(-1), and the detection limit is 0.0946 microg x L(-1). The instrumental relative standard deviation is about 0.55% and the recovery is about 94%-107%. The method is accurate, rapid and convenient with satisfactory results.

[Study on extraction separation of Bi(III), Fe(III), Cu(II), Ni(II), Co(II) and Pb(II) in PEG-(NH4)2SO4-PR system using spectrophotometry].

In polyethylene PEG-(NH4)2SO4-PR system the extraction separation behaviour of the complexes of Bi(III), Fe(III), Cu(II), Ni(II), Co(II) and Pb(II) was investigated. The results indicated that Bi in pH 3.5-6.5 and Fe(III) in pH 4.0-7.0 were almost completely extracted by the PEG phase, while Cu(II) and Co(II) in pH 1.0-7.0, Pb(II) in pH 2.0-7.0, and Ni(II) in pH 1.0-4.5 were not extracted by the PEG phase. So Bi(III) (pH 3.5) and Fe(III) (pH 5.0) were quantitatively separated from the mixed solution of Bi(III), Fe(III), Cu(II), Co(II), Pb(II) and Ni(II) ions. The extraction mechanism for PEG phase was preliminarily studied.

Radiochemical separation of carrier-free 204,206 Bi from alpha-irradiated thallium oxide target.

Alpha activation of Tl(2)O(3) target results in the formation of carrier-free 204,206 Bi. Two different radiochemical methods were used for the separation of bismuth radionuclides from the target matrix. A very high separation factor was achieved using liquid-liquid extraction (LLX) method with methyl isobutyl ketone (MIBK)-HCl system. Solid-liquid exchange adsorption was carried out using a novel inorganic ion exchanger, zirconium vanadate from HCl medium. The separation was found to be maximum around pH 2.

Breakthrough of 225Ac and its radionuclide daughters from an 225Ac/213Bi generator: development of new methods, quantitative characterization, and implications for clinical use.

Bisumth-213, a short-lived alpha particle emitting radionuclide, is generated from the decay of 225Ac, which has a half-life of 10 days. The development of a clinical 225Ac/213Bi generator and the preparation of a 213Bi radiolabeled antibody for radioimmunotherapy of leukemia have been reported. The 225Ac decay scheme is complex; therefore a thorough understanding of the impact of both the parent 225Ac and its daughters on radiolabeling, purification, and quantification is necessary for optimal use of the generator system. This paper reports: (i) unique new methods to measure 221Fr, 213Bi, and 209Pb, the prominent daughters of 225Ac; and (ii) a quantitative evaluation of 225Ac/213Bi generator breakthrough and the radionuclidic purity of 213Bi labeled radiopharmaceutical dose formulations. A quantitative multi-dimensional proportional scanning method was employed to distinguish and measure specific daughter radionuclides. This method combines thin layer chromatography in two perpendicular directions with attenuated collimation as a function of time for data collection and analysis. Francium-221 and 213Bi eluted differentially from the generator, and 221Fr contributed minimally to unchelated 213Bi in the reaction and final products. Lead-209 was present in the reaction solution, but not strongly bound by the chelating moiety either (i) under the 213Bi labeling reaction conditions or (ii) following chelated 213Bi decay. As a consequence of incorporating several new procedures to the operation of the generator, 225Ac breakthrough in the final product was further reduced and represented a trivial contaminant in the final drug formulations.

Rapid preparation of short-lived alpha particle emitting radioimmunopharmaceuticals.

Alpha emitting radionuclides are of considerable interest for targeted radioimmunotherapy. Generator supplied 213Bi emitting 8.5 MeV alpha particles with a 45.6 min half-life has been conjugated to a monoclonal antibody (HuM195-CHX-A-DTPA) for targeted therapy of leukemia in a clinical trial. The clinical dose preparation of pharmaceutical formulation by a pair of skilled radiochemists took 25 min, which corresponds, to an overall decay loss of 30% of the initial 213Bi activity eluted from the generator. In order to allow more widespread and practical clinical use of targeted 213Bi alpha particle therapy, we developed a new procedure that is simpler, more rapid and adaptable to a hospital pharmacy. The new 10 min process includes a tandem elution and labeling, and an anion exchange column purification method that can be reproducibly used.

Evaluation of an internal cyclotron target for the production of 211At via the 209Bi (alpha,2n)211 at reaction.

Astatine-211 is a 7.2 h half-life alpha-emitting radionuclide which has shown great promise for targeted radiotherapy. It is generally produced by cyclotron bombardment of bismuth metal targets with 28 MeV alpha-particles via the 209Bi(alpha,2n)211 At reaction. In order to provide 211At activity levels anticipated for clinical investigations, an internal target system has been designed and evaluated. The system has a grazing-angle configuration and leading- and trailing-edge monitors. Both aluminum and copper target backings were evaluated. With approx. 28 MeV alpha-particles, the 211At production efficiency was 41 +/- 7 MBq/microA.h, compared with 10.6 +/- 1.2 MBq/microA.h for an external target. Radionuclidic purity of 211At was high with no evidence of 210At.