Rapid isolation of plutonium in environmental solid samples using sequential injection anion exchange chromatography followed by detection with inductively coupled plasma mass spectrometry

This paper reports an automated analytical method for rapid determination of plutonium isotopes (²³⁹Pu and ²⁴⁰Pu) in environmental solid extracts. Anion exchange chromatographic columns were incorporated in a sequential injection (SI) system to undertake the automated separation of plutonium from matrix and interfering elements. The analytical results most distinctly demonstrated that the crosslinkage of the anion exchanger is a key parameter controlling the separation efficiency. AG 1-×4 type resin was selected as the most suitable sorbent material for analyte separation. Investigation of column size effect upon the separation efficiency revealed that small-sized (2 mL) columns sufficed to handle up to 50 g of environmental soil samples. Under the optimum conditions, chemical yields of plutonium exceeded 90% and the decontamination factors for uranium, thorium and lead ranged from 10³ to 10⁴. The determination of plutonium isotopes in three standard/certified reference materials (IAEA-375 soil, IAEA-135 sediment and NIST-4359 seaweed) and two reference samples (Irish Sea sediment and Danish soil) revealed a good agreement with reference/certified values. The SI column-separation method is straightforward and less labor intensive as compared with batch-wise anion exchange chromatographic procedures. Besides, the automated method features low consumption of ion-exchanger and reagents for column washing and elution, with the consequent decrease in the generation of acidic waste, thus bearing green chemical credentials.     

Portable formaldehyde monitoring device using porous glass sensor and its applications in indoor air quality studies

We have developed a portable device for formaldehyde monitoring with both high sensitivity and high temporal resolution, and carried out indoor air formaldehyde concentration analysis. The absorbance difference of the sensor element was measured in the monitoring device at regular intervals of, for example, one hour or 30 min, and the result was converted into the formaldehyde concentration. This was possible because we found that the lutidine derivative that was formed as a yellow product of the reaction between 1-phenyl-1,3-butandione and formaldehyde was stable in porous glass for at least six months. We estimated the reaction rate and to be 0.049 min⁻¹ and the reaction occurred quickly enough for us to monitor hourly changes in the formaldehyde concentration. The detection limit was 5 μg m⁻³ h. We achieved hourly formaldehyde monitoring using the developed device under several indoor conditions, and estimated the air exchange rate and formaldehyde adsorption rate, which we adopted as a new term in the mass balance equation for formaldehyde, in one office.     

On-chip pre-concentration and complexation of [¹⁸F]fluoride ions via regenerable anion exchange particles for radiochemical synthesis of Positron Emission Tomography tracers

Microfluidic approaches have demonstrated a relevant impact on radiochemical reactions involving Positron Emission Tomography (PET) nuclides, due to shorter reaction times and smaller precursor quantities. However, little attention has been given to the integration of the initial pre-concentration and drying of radioactive [(18)F]fluoride ions, required for the labeling of radiotracer compounds. In this work we report the design, fabrication and implementation of a glass microfluidic device filled with recyclable anion exchange particles for the repeated recovery of [(18)F] and [(19)F]fluoride ions. The device was first tested with non radioactive [(19)F]fluoride ions and it was shown to repeatedly trap and elute >95% fluoride over 40 successive experimental runs with no decrease in efficiency. The same device was then tested for the trapping and release of [(18)F]fluoride ions over 20 experiments with no measurable decrease in performance. Finally, the [(18)F]fluoride ions were eluted as a K(18)F/K2.2.2 complex, dried by repeated dissolution in acetonitrile and evaporation of residual water, and reacted with ethyl ditosylate (EtDT) leading to the desired product ([(18)F]fluoroethyltosylate) with 96 ± 3% yield (RCY). The overall time needed for conditioning, trapping, elution and regeneration was less than 6 min. This approach will be of great benefit towards an integrated platform able to perform faster and safer radiochemical synthesis on the micro-scale.     

Novel molecularly imprinted polymer using 1-(α-methyl acrylate)-3-methylimidazolium bromide as functional monomer for simultaneous extraction and determination of water-soluble acid dyes in wastewater and soft drink by solid phase extraction and high performance liquid chromatography

Novel water-compatible molecularly imprinted polymers were synthesized in methanol-water systems with Tratarzine as template and 1-(α-methyl acrylate)-3-methylimidazolium bromide (1-MA-3MI-Br) as functional monomer, which has π-π hydrophobic, hydrogen-bonding and electrostatic interactions with template molecule. 1-MA-3MI-Br molecularly imprinted polymers (1-MA-3MI-Br-MIPs) were used as selective sorbents for the solid-phase extraction (SPE) of water-soluble acid dyes from wastewater and soft drink. The good linearity of the method was obtained in a range of 5.0-2000 μg/L with the correlation coefficient of > 0.999. The detection limits were in a range of 0.13-0.51 μg/L for the water-soluble acid dyes in wastewater and 0.095-0.84 μg/L for those in soft drink. The mean recoveries for the acid dyes are from 89.1% to 101.0% in spiked wastewater and 91.0-101.3% in spiked soft drink. Compared with strongly anion exchange solid phase extraction (SAX-SPE), mixture anion exchange solid phase extraction (MAX-SPE), and 1-MA-3MI-Br non-imprinted solid phase extraction (1-MA-3MI-Br-NISPE), almost all of the matrix interferences were removed by 1-MA-3MI-Br-MISPE, exhibiting higher selectivity, recovery and enrichment ability for the acid dyes and better baselines in the results of HPLC analysis.     

液相色谱-串联质谱法快速测定植物源性食品中的百草枯

建立了水果、蔬菜、豆类和粮谷中百草枯残留的高效液相色谱-串联质谱(HPLC-MS/MS)分析方法.用水提取样品中的百草枯,弱阳离子交换(WCX)固相萃取柱(SPE)净化.采用CAPCELL PAK ST色谱柱(150 mm×2.0mm).乙腈-10 mmol/L乙酸铵水溶液(用甲酸调至pH 4.0)为流动相,以电喷雾离...     

锂离子交换体Li1.5Ti1.625O4的研究(Ⅱ)-H1.5Ti1.625O4的交换性能研究

本文就H1.5Ti1.625O4的pH滴定、分配系数Kd、交换容量、交换等温线、交换速度等离子交换性能进行了研究.研究结果表明,H1.5Ti1.62504对锂离子表现出很好的离子交换选择性及记忆性交换功能.     

凝结水精处理阳树脂硫酸根溶出特性研究

电站给水系统中存在微量的SO42-就会对金属材料造成严重腐蚀。针对目前凝结水精处理系统投运后导致核电站蒸汽发生器或炉水中SO42-含量升高的问题,采用动态循环溶出和静态浸泡的方法对几种凝结水精处理常用阳树脂的SO42-溶出行为进行了研究。结果表明,不同树脂的SO42-溶出行为有较大差异,SO42-含量在短时间内随时间增长呈上升趋势,新树脂溶出SO42-的量比旧树脂大得多。通过对溶出液进行高温和氧化处理,发现溶出物中还含有一些有机磺酸盐,它们在高温或氧化条件下会分解产生SO42-和酸性物质。     

Surface modification of hydrophobic NaYF_4:Yb,Er upconversion nanophosphors and their applications for immunoassay

β-NaYF4:Yb,Er upconversion nanophosphor (UCNP) is known as one of the most efficient NIR-to-visible upconversion materials, which shows great potential in bioanalytical chemistry and bioimaging. However, its applications are greatly limited due to its low water dispersibility and thus poor biocompatibility. In this paper, poly(acrylic acid) (PAA)-based ligand exchange strategies are carried out to modify oleic acid-capped hydrophobic β-NaYF4:Yb,Er UCNPs into hydrophilic ones. After efficient surface modific...     

Morphological investigations of block sulfonated poly(arylene ether ketone) copolymers as potential proton exchange membranes

A series of block sulfonated poly(arylene ether ketone) (SPAEK) copolymers with different block lengths and ionic contents were synthesized by a two‐stage process. The morphology of these block SPAEK copolymers was investigated by various methods, such as differential scanning calorimetry (DSC), transmission electron microscope (TEM), and small angle X‐ray scattering (SAXS). Dark colored ionic domains of hundreds of nanometers spreading as a cloud‐like belt were observed in TEM images. The sizes of the ionic domains as a function of block copolymer composition were determined from SAXS curves. The results for the evolution of ionic domains revealed that the block copolymers exhibited more clearly phase‐separated microstructure with increasing ionic contents and hydrophobic sequence lengths. Proton conductivity is closely related to the microstructure, especially the presence of large interconnected ionic domains or ionic channels. Block SPAEK membranes have interconnected ionic clusters to provide continuous hydrophilic channels, resulting in higher proton conductivity. Copyright © 2010 John Wiley & Sons, Ltd.     

Formation of metal complex ions from amino acid in the presence of Li+, Na+ and K+ by electrospray ionization: metal replacement of hydrogen in the ligands

Alkali metal cations easily form complexes with proteins in biological systems; understanding amino acid clusters with these cations can provide useful insight into their behaviors at the molecular level including diagnosis and therapy of related diseases. For the purpose of characterization of basic interaction between amino acids and alkali metal, each of the 20 naturally occurring amino acids were ionized in the presence of lithium, sodium and potassium cations by electrospray ionization, and the resulting product ions were analyzed. We focus our attention on the gas phase alkali metal ion-proton exchanged complexes in current study, specifically complexes with serine, threonine, asparagine and glutamine, which share characteristic pattern unlike other amino acids. All amino acids generated [M + H](+) and [M + Na](+) ions, where M stands for the neutral amino acid. Serine, threonine, asparagine and glutamine generated cluster ions of [nM - nH + (n + 1)Na](+) and [nM - (n - 1)H + (n - 1)Na + K](+) , where n = 1-7. While the (M - H + Li) and (M - H + K) species were not observed, the neutral (M - H + Na) species formed by proton-sodium cation exchange had a highly stable cyclic structure with ketone and amine ligand sites, suggesting that (M - H + Na) serves as a building block in cluster ion formation. Cluster ion intensity distributions of [nM - nH + (n + 1)Na](+) and [nM - (n - 1)H + (n - 1)Na + K](+) showed a magic number at n = 3 and 4, respectively. Extensive B3LYP-DFT quantum mechanical calculations were carried out to elucidate the geometry and energy of the cluster ions, and they provided a reasonable explanation for the stability and structure of the cluster ions.