Ion exchange chromatography coupled to inductively coupled plasma mass spectrometry for the study of Pt electro-dissolution

There is an ongoing debate regarding the mechanism of Pt electrochemical dissolution. However, only off-line methods have so far been used, where separation of Pt species is performed separately from their detection. In this study, ion exchange chromatography coupled to inductively coupled plasma mass spectrometry was used for the first time to separate and detect Pt species generated by the electro-dissolution of a Pt electrode in 0.5 M aqueous H₂SO₄ solution. Because these species are either neutral or cationic, they were converted to chloro-complexes using 0.1 M KCl to enable their separation by anion exchange chromatography. Chloro-aqua complexes were observed in addition to the two predominant species, namely PtCl₄²⁻ and PtCl₆²⁻. A good linear relationship was observed between the sum of peak areas for all complexes of a given Pt oxidation state and the Pt concentration, with a detection limit of 0.1 μg L⁻¹ being reached for Pt(II) and Pt(IV). Application of this speciation analysis method to real samples generated by potential cycling using cyclic voltammetry (CV) revealed that, in general, at least 80% of Pt was present as Pt(II), irrespectively of the cyclic potential range or of temperature (up to 60 °C). Still, quantitative spike recovery was achieved after adding known amounts of Pt(II) or Pt(IV) to a sample prepared by CV, which demonstrated that no significant species inter-conversion took place.     

Synthesis Of 2-Acyltetrahydro-β-Carbolines By An Intramolecular α-Amidoalkylation Reaction

2-Acyltetrahydro-β-carbolines 7 have been obtained by cyclization of adducts 5 from imines 3 of tryptamine 1 and aldehydes 2 with acyl chlorides 4 as a result of an intramolecular a-amidoalkylation reaction in the presence of bases as N,N-dimethylaniline or Et₃N.     

Advances in arsenic speciation techniques

The present review describes the speciation techniques of arsenic. The principal advanced techniques discussed are gas chromatography, reversed-phase liquid chromatography, ion chromatography, capillary electrophoresis. Some other techniques are also mentioned. The extraction procedures of arsenic species from unknown samples are also discussed. Arsenic speciation is summarized in tabular form and optimizing parameters are also discussed.     

Synthesis,characterisation and ion exchange properties of hybrid organic–inorganic composite material: polyacrylamide zirconium (IV) iodosulphosalicylate

ABSTRACT

Contamination of groundwater by heavy metal is one of the most emerging and serious environmental problems. There are so many methods which are available to overcome these problems. Among various available methods, hybrid organic–inorganic ion exchange resin has become more popular due to certain advantages over other available conventional methods; hence, in the present proposed work, we synthesised a hybrid organic–inorganic composite material polyacrylamide zirconium (IV) iodosulphosalicylate by using the sol-gel technique. Synthesised resin was characterised by various methods like Infrared spectroscopy and Thermogravimetric analysis-Differential thermal analysis. Various samples of this ion exchange resin are prepared by changing the condition of synthesis, i.e. concentration of acrylamide to rationalise the ion exchange capacity of the synthesise hybrid organic–inorganic ion exchange resins. A mixture of 0.1 M potassium iodate, 0.1 M sulphosalicylic acid and 0.1 M acrylamide was added dropwise to 0.4 M zirconium oxychloride accompanied by constant stirring for 8 h using magnetic stirrer at 70°C to yield polyacrylamide zirconium (IV) iodosulphosalicylate with maximum ion exchange capacity. Ion exchange capacity of synthesised resin was determined by column method and the maximum ion exchange capacity was found for Pb(II). Determination of k_d values shows that the resin was highly selective for Pb (II).The selectivity for Pb was also evaluated by using certain binary mixture separation such as Ni (II)-Pb(II), Cu(II)-Pb(II), Cd(II)-Pb(II), Sr(II)-Pb(II), Ba(II)-Pb(II),Zn(II)-Pb(II) and Mg(II)-Pb(II).     

Isolation and Structure Characterization of a (4‐O‐Methyl‐d‐glucurono)‐d‐xylan from the Skin of Opuntia ficus‐indica Prickly Pear Fruits

A slightly water soluble (4‐O‐methyl‐d‐glucurono)‐d‐xylan was isolated from the skin of Opuntia ficus‐indica (OFI) fruits by alkaline extraction, followed by ethanol precipitation and ion‐exchange chromatography. The structure of this xylan was determined by sugar determination coupled with a ¹H and ¹³C NMR spectroscopy analysis. The xylan consisted of a linear (1→4)‐β‐d‐xylopyranosyl backbone decorated with 4‐O‐methyl‐α‐d‐glucopyranosyluronic acid groups linked to the C‐2 of the xylopyranosyl residues, in the ratio of one uronic acid for six neutral sugar units.     

Extraction of methocarbamol from human plasma with a polypyrrole/multiwalled carbon nanotubes composite decorated with magnetic nanoparticles as an adsorbent followed by electrospray ionization ion mobility spectrometry detection†

In this work, a polypyrrole/multiwalled carbon nanotubes composite decorated with Fe₃O₄ nanoparticles was chemically synthesized and applied as a novel adsorbent for the extraction of methocarbamol from human plasma. Electrospray ionization ion mobility spectrometry was used for the determination of the analyte. The properties of the magnetic‐modified adsorbent were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform IR spectroscopy, and X‐ray diffraction. The effects of experimental parameters on the extraction efficiency of the sorbent were investigated. Under the optimized conditions, the linear dynamic range was found to be 2–150 ng/mL with the detection limit of 0.9 ng/mL. The relative standard deviation was 5.3% for three replicate measurements of methocarbamol in plasma sample. The extraction efficiency of the sorbent for the determination of different drugs with various polarities was also compared to that of Fe₃O₄‐polypyrrole and Fe₃O₄‐multiwalled carbon nanotubes sorbents. Finally, the method was used for the determination of methocarbamol in blood samples.     

Static headspace‐multicapillary column with gas chromatography coupled to ion mobility spectrometry as a simple approach for the discrimination of crude and processed traditional Chinese medicines

The processing procedure can alter the nature and chemical transformation of traditional Chinese medicine to accommodate different clinical dispensing and preparation requirements. In this study, static headspace‐multicapillary column with gas chromatography coupled to ion mobility spectrometry was developed for the rapid and sensitive discrimination of crude and processed traditional Chinese medicine. Using Radix Paeoniae Alba as a traditional Chinese medicine model, the combined power of this approach was illustrated by classifying the crude and processed Radix Paeoniae Alba samples into two main categories. The contents of the main components in Radix Paeoniae Alba varied significantly. The established method could promote the use of ion mobility spectrometry in intrinsic quality control and differentiation of herbal medicines from other processed products or preparations.     

Pure Ion Chromatograms Combined with Advanced Machine Learning Methods Improve Accuracy of Discriminant Models in LC–MS-Based Untargeted Metabolomics

Untargeted metabolomics based on liquid chromatography coupled with mass spectrometry (LC–MS) can detect thousands of features in samples and produce highly complex datasets. The accurate extraction of meaningful features and the building of discriminant models are two crucial steps in the data analysis pipeline of untargeted metabolomics. In this study, pure ion chromatograms were extracted from a liquor dataset and left-sided colon cancer (LCC) dataset by K-means-clustering-based Pure Ion Chromatogram extraction method version 2.0 (KPIC2). Then, the nonlinear low-dimensional embedding by uniform manifold approximation and projection (UMAP) showed the separation of samples from different groups in reduced dimensions. The discriminant models were established by extreme gradient boosting (XGBoost) based on the features extracted by KPIC2. Results showed that features extracted by KPIC2 achieved 100% classification accuracy on the test sets of the liquor dataset and the LCC dataset, which demonstrated the rationality of the XGBoost model based on KPIC2 compared with the results of XCMS (92% and 96% for liquor and LCC datasets respectively). Finally, XGBoost can achieve better performance than the linear method and traditional nonlinear modeling methods on these datasets. UMAP and XGBoost are integrated into KPIC2 package to extend its performance in complex situations, which are not only able to effectively process nonlinear dataset but also can greatly improve the accuracy of data analysis in non-target metabolomics.     

二维材料用于渗透能转换的研究进展

在河水与海水的交界处实现渗透能提取与捕获是解决未来能源危机的重要方式之一. 渗透能因为储量大, 容易获取以及绿色可持续的优势受到广泛关注. 反向电渗析技术是一种能够有效捕获渗透能的方法之一, 目前已经得到了深入的研究与发展. 离子交换膜是反向电渗析技术转换渗透能的关键组件, 其性能的优异程度决定能量转换效率的高低. 常见的膜材料主要是高分子聚合物及其改性化合物, 最近一些二维材料如石墨烯、 氧化石墨烯、 二硫化钼、 各种框架材料及其改性复合物因优异的选择性离子传输、 纳米级通道、 丰富的表面功能基团以及可修饰性成为捕获渗透能的重要膜材料. 本文综合评述了二维材料作为离子传输通道的类型以及相应的传输机理; 例举了二维材料及其复合物的设计方案和在渗透能转换方面的具体应用; 最后提出了目前二维材料在渗透能转换领域中面临的挑战以及未来的发展方向.     

On a new FeOF polymorph: Synthesis and stability

A new polymorph of FeOF (up to now only known in its rutile type structure) was prepared by using a new synthesis approach formally based on anionic exchange using the well-known layered FeOCl as precursor. The synthesis was achieved using [CH₃C(CH₂O–)₂(COO–)B] to vehicle fluorine through the formation of soluble (CH₃)₄N⁺ [CH₃C(CH₂O–)₂(COO–)BF]⁻ and using N,N-dimethylformamide (DMF) as the reacting medium. The XRD pattern of layered FeOF can be indexed with an orthorhombic cell which doubles along the b axis (which is the direction perpendicular to the layers) with respect to that of pristine FeOCl (a = 3.792(1) Å, b = 12.699(1) Å, c = 3.321(1) Å). Both thermal analysis and diffraction indicate similar stability for the layered and rutile polymorphs. Such findings are rationalized through Density Functional Theory calculations. It is found that the energy difference between the more stable rutile and layered polymorphs is practically nul. The origin of the similar stability lies in the fact that although the number of Fe–F and Fe–O bonds is different in the two structures, the strength of both the total number of Fe–O as well as Fe–F bonds are found to be almost identical. Even if the crystal and electronic structures are considerably different, the total bonding and thus, the stability of the two polymorphs, is comparable. The stability of different FeOF rutile type structures is also analyzed.