Reverse-Polarization High-Performance Layer Electrochromatography-A New Approach to Anion Separation.

High-performance layer electrochromatography (HPLEC) combines the advantages of overpressured-layer chromatography (OPLC) and pressurized planar electrochromatography (PPEC) while overcoming some of their limitations. HPLEC equipment can work in various HPLEC, OPLC, and PPEC modes. The equipment enables HPLEC analysis also with an electroosmotic effect directed against the hydrodynamic flow of the mobile phase. The change in the electric field direction in the separation system does not result in a change in either the direction of the mobile phase flow or the direction of solute migration. The hydrodynamic flow generated by the pump dominates the electroosmotic effect and enables separation against the direction of the latter. Reversed-polarization HPLEC may be advantageous for the analysis of anionic compounds, as it facilitates faster and more selective separation than OPLC performed in similar conditions. This separation mode provides a new possibility to develop and optimize separation methods by performing separation against the electroosmotic effect and without need of any modification of the adsorbent surface. A drawback of this separation mode is the increase in the backpressure at the mobile phase inlet and the limitation of the mobile phase flow rate. Currently, contrary to the single-channel mode, multi-channel reverse-polarity HPLEC still requires some technical and methodological improvements.

Picking on Carbonate: Kinetic Selectivity in the Encapsulation of Anions.

Supramolecular hosts bind to inorganic anions at a fast rate and select them in proportion with thermodynamic stability of the corresponding [anion⊂host] complexes, forming in a reversible manner. In this study, we describe the action of hexapodal capsule 1 and its remarkable ability to select anions based on a large span of rates by which they enter this host. The thermodynamic affinity of 1 toward eighteen anions extends over eight orders of magnitude (0

Selective Separation of Hexachloroplatinate(IV) Dianions Based on Exo-Binding with Cucurbit[6]uril.

The recognition and separation of anions attracts attention from chemists, materials scientists, and engineers. Employing exo-binding of artificial macrocycles to selectively recognize anions remains a challenge in supramolecular chemistry. We report the instantaneous co-crystallization and concomitant co-precipitation between [PtCl6 ]2- dianions and cucurbit[6]uril, which relies on the selective recognition of these dianions through noncovalent bonding interactions on the outer surface of cucurbit[6]uril. The selective [PtCl6 ]2- dianion recognition is driven by weak [Pt-Cl⋅⋅⋅H-C] hydrogen bonding and [Pt-Cl⋅⋅⋅C=O] ion-dipole interactions. The synthetic protocol is highly selective. Recognition is not observed in combinations between cucurbit[6]uril and six other Pt- and Pd- or Rh-based chloride anions. We also demonstrated that cucurbit[6]uril is able to separate selectively [PtCl6 ]2- dianions from a mixture of [PtCl6 ]2- , [PdCl4 ]2- , and [RhCl6 ]3- anions. This protocol could be exploited to recover platinum from spent vehicular three-way catalytic converters and other platinum-bearing metal waste.

Framework Cationization by Preemptive Coordination of Open Metal Sites for Anion-Exchange Encapsulation of Nucleotides and Coenzymes.

Cationic frameworks can selectively trap anions through ion exchange, and have applications in ion chromatography and drug delivery. However, cationic frameworks are much rarer than anionic or neutral ones. Herein, we propose a concept, preemptive coordination (PC), for targeting positively charged metal-organic frameworks (P-MOFs). PC refers to proactive blocking of metal coordination sites to preclude their occupation by neutralizing ligands such as OH(-) . We use 20 MOFs to show that this PC concept is an effective approach for developing P-MOFs whose high stability, porosity, and anion-exchange capability allow immobilization of anionic nucleotides and coenzymes, in addition to charge- and size-selective capture or separation of organic dyes. The CO2 and C2 H2 uptake capacity of 117.9 cm(3) g(-1) and 148.5 cm(3) g(-1) , respectively, at 273 K and 1 atm, is exceptionally high among cationic framework materials.

Efficient separation of organic anions in beverages using aminosilane-functionalized capillary electrophoresis with contactless conductivity detection.

BACKGROUND: Capillary electrophoresis (CE) has the advantage of rapid anion analysis, when employing a reverse electroosmotic flow (EOF). The conventional CE method utilizes dynamic coatings with surfactants like cetyltrimethylammonium bromide (CTAB) in the run buffer to reverse the EOF. However, this method suffers from very slow equilibration leading to drifting effective migration times of the analyte anions, which adversely affects the identification and quantification of peaks. Permanent coating of the capillary surface may obviate this problem but has been relatively little explored. Thus, permanent capillary surface modification by the covalent binding of 3-aminopropyltriethoxysilane (APTES) was studied as an alternative. RESULTS: This study investigates the effect of APTES concentration for surface functionalization on EOF mobility, separation efficiency, and reproducibility of anion separation. The performance data was complemented by X-ray photoelectron spectroscopy (XPS) and contact angle (CA) measurements. The XPS measurements showed that the coverage with APTES was dependent on its concentration in the coating solution. The XPS measurements correlated well with the EOF values determined for the capillaries tested. A standard mixture of 21 anions could be baseline separated within 10 min in the capillaries with lower EOF, but not in the capillary with the highest EOF as the residence time of the analytes was too short in this case. Compared to conventional dynamic coating with CTAB, APTES-functionalized capillaries provide faster equilibration and long-term EOF stability. The application of APTES-functionalized capillaries in analyzing different beverages demonstrates the precision, reliability, and specificity in determining organic anions, providing valuable insights of their compositions. SIGNIFICANCE: APTES coating on capillaries provides a facile approach to achieve a permanent reversal of the stable EOF to determine anions. The control of the coverage via the concentration of the reagent solution allows the tailoring of the EOF to different needs, a faster EOF for less complex samples where resolution is not challenging, while a lower EOF for higher complex samples where the focus is on separation efficiency. This enhancement in efficiency and sensitivity has been applied to analyzing organic acids in several beverages.

Radiochemical quality control of the radiopharmaceutical, 89SrCl2 produced in FBTR.

89SrCl2 radiopharmaceuticals is mainly used for bone pain palliation in the cancer patients, is being produced in FBTR via 89Y(n, p)89Sr using yttria target. The irradiated yttria target is chemically processed in high pure quartz distilled nitric acid medium in hot cell facility, to avoid the corrosion of components of hotcell due to chloride ions while using HCl medium. Being ionic species, the purified 89Sr(II) cation in aqueous solution containing bulk nitrate and other trace anions, exists as SrXn species where X: F-, Cl-, Br-, NO3-, PO43- and SO42-, n: stoichiometric anion content. The aim of the manuscript is to standardise an efficient ultra-low level anion purification method (ppb range) for the conversion of SrXn to SrCl2 and estimate the residual anionic impurities as recommended by the appropriate source specifications for its medical application. Various methods were standardised for the removal of anions in the SrCl2 source produced by the above process which include evaporation, calcination, anion exchange column, cation exchange column as well as its combination with pre-concentration column of ion chromatography (IC) technique using 89Sr tracers as well as FBTR produced 89Sr solution. Assay of 89Sr and other anions including nitrate for the above study were accomplished using Cerenkov counting and ion chromatography respectively. Thus evaporation-calcination-column chromatography mode was finalised to obtain pure SrCl2 source free from nitrate and other anionic impurities. This is the first ever systematic study for the Radiochemical quality control of nca 89SrCl2 radiopharmaceutical produced in a fast reactor. This study also finds its application to any analytical lab as well as industry where there is a requirement of anion purification in the ppb level.

Retention of inorganic anions using mesoporous zirconia spheres modified with anion-exchange groups as the stationary phase for ion chromatography.

A zirconia (ZrO2) stationary phase with a chemically fixed silane coupling agent (trimethyl [3-(trimethoxysilyl)propyl]ammonium chloride; TMA), which possesses quaternary ammonium functional groups, is evaluated as a separation column for ion chromatography (IC) of anions. The selectivity for anions varies depending on the amount of TMA immobilized on the ZrO2. The TMA-ZrO2, with an anion-exchange capacity of 17 ± 3 µeq/g, shows an anion-exchange reaction that involves the specific retention of fluoride ion on ZrO2. The TMA-ZrO2 exhibits a decrease of the anion resolution with an increase of the eluent pH and an enhancement of the selective separation of fluoride ion with an increase of the column temperature. Through this study, the TMA-ZrO2 stationary phase shows potential as a new medium for ion separation.

Subnanometer Ion Channel Anion Exchange Membranes Having a Rigid Benzimidazole Structure for Selective Anion Separation.

Ion-conductive polymers having a well-defined phase-separated structure show the potential application of separating mono- and bivalent ion separation. In this work, three side-chain-type poly(arylene ether sulfone)-based anion exchange membranes (AEMs) have been fabricated to investigate the effect of the stiffness of the polymer backbone within AEMs on the Cl-/NO3- and Cl-/SO42- separation performance. Our investigations via small-angle X-ray scattering (SAXS), positron annihilation, and differential scanning calorimetry (DSC) demonstrate that the as-prepared AEM with a rigid benzimidazole structure in the backbone bears subnanometer ion channels resulting from the arrangement of the rigid polymer backbone. In particular, SAXS results demonstrate that the rigid benzimidazole-containing AEM in the wet state has an ion cluster size of 0.548 nm, which is smaller than that of an AEM with alkyl segments in the backbone (0.760 nm). Thus, in the electrodialysis (ED) process, the former exhibits a superior capacity of separating Cl-/SO42- ions relative to latter. Nevertheless, the benzimidazole-containing AEM shows an inability to separate the Cl-/NO3- ions, which is possibly due to the similar ion size of the two. The higher rotational energy barrier (4.3 × 10-3 Hartree) of benzimidazole units and the smaller polymer matrix free-volume (0.636%) in the AEM significantly contribute to the construction of smaller ion channels. As a result, it is believed that the rigid benzimidazole structure of this kind is a benefit to the construction of stable subnanometer ion channels in the AEM that can selectively separate ions with different sizes.

Unexpected separate elution of cation and anion of an ammonium salt in supercritical fluid chromatography.

Amines are frequently used as additives in supercritical fluid chromatography (SFC). They allow eluting basic analytes with reasonable retention times and less distorted peak shapes. Since amines are chemically active compounds, their introduction into SFC mobile phase always raises a question on whether they can react with analytes or mobile phase constituents and, if so, can it affect chromatography separation. Primary and secondary amines are known to react with carbon dioxide, also all amines, being bases, can interact with CO2-alcohol mixtures which are known to be slightly acidic. In this work, we report a case of separate elution of an ammonium salt, salbutamol sulfate, anion and cation in SFC. Retention time of a peak which molecular mass registered by mass-spectrometry in ES(-) mode corresponds to HSO4- differs substantially from the retention time of a peak corresponding to salbutamol [M+H] registered in ES(+) regime. Moreover, sulfate anion retention time depends both on amine additive type and concentration whereas salbutamol retention time doesn't. Similar effect is observed on other columns as well as with other ammonium salts. We suppose that such behavior is caused by the exchange chemical reaction happening between ammonium salt analyte and amine additive. An additive converts a salt into a free base form and turns into a salt form itself. If this hypothesis is true, it might be important to take the possibility of such interactions into account during preparative SFC work since the compound injected might not be equivalent to a compound eluted.