HPLC Stationary Phase Research Articles

A novel homochiral metal–organic framework with an expanded open cage based on (R)-3,3′-bis(6-carboxy-2-naphthyl)-2,2′-dihydroxy-1,1′-binaphthyl: synthesis, X-ray structure and efficient HPLC enantiomer separation

A new homochiral MOF with an expanded open cage was synthesized and utilized as a chiral stationary phase for HPLC.

Helicity induction and memory effect in poly(biphenylylacetylene)s bearing various functional groups and their use as switchable chiral stationary phases for HPLC

Poly(biphenylylacetylene)s bearing various functional groups were demonstrated to be used as elution order switchable chiral stationary phases for HPLC.

A biomimetic hybrid material consisting of CaCO3 mesoporous microspheres and an alternating copolymer for reversed-phase HPLC.

We developed a biomineral-inspired hybrid material composed of CaCO3 and an organic polymer as a column packing material for HPLC. This material combines a hierarchical mesoporous structure and the functionality of the polymer. The surface of monodispersed mesoporous CaCO3 microspheres was modified with poly(maleic acid-alt-1-octadecene) (PMAcO) comprising hydrophobic alkyl chains and anionic carboxylate groups. PMAcO adsorbed onto the surface of CaCO3 through electrostatic interaction between Ca2+ sites and carboxylate groups, resulting in an octadecene coated microsphere interface. These microspheres were applied as a HPLC column and exhibited reversed-phase retention behavior in the separation of alkylbenzenes. This column showed high alkaline mobile phase resistance compared with the conventionally applied ODS column packing material. Quantitative analysis of the basic antidepressants clomipramine and imipramine spiked into whole blood was achieved with an alkaline mobile phase, demonstrating the potential of the biomineral-inspired material as a HPLC stationary phase for practical applications in routine analyses of basic drugs requiring alkaline mobile phases.

Preparation and evaluation of surface-bonded phenylglycine zwitterionic stationary phase.

4-Hydroxy-D-phenylglycine was modified with methacrylic anhydride and then immobilized on silica through thiol-initiated surface polymerization; the prepared material was applied as stationary phase for HPLC. The obtained stationary phase was characterized by elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The chromatographic performance of the packed column was evaluated in reversed-phase liquid chromatograph (RPLC) and hydrophilic interaction liquid chromatograph (HILIC) mode; this column has shown excellent selectivity to both the hydrophobic and hydrophilic solutes. The selectivity towards polycyclic aromatic hydrocarbons relative to that towards alkylbenzenes exhibited by the prepared column was higher than the corresponding selectivity exhibited by commercial C18 column, which could be explained by electronic π-π interaction between phenylglycine and electron-rich aromatic rings. On the other hand, the prepared column has also shown better selectivity for polar compounds, which was based on the multiple interaction and retention mechanisms. It was also used to separate sulfonamides and organic acid compared with a commercial C18 and HILIC column; the results show its great chromatographic performance with distinctive selectivity. All the results indicated the prepared column had potential application in a wide range.

Editorial: Advanced Stationary Phases for HPLC

Editorial: Advanced Stationary Phases for HPLC

Silica Hydride-Based Packing Materials: HPLC Stationary Phases for a Global Approach to Complex Sample Analysis

Silica Hydride-Based Packing Materials: HPLC Stationary Phases for a Global Approach to Complex Sample Analysis

Preparation and evaluation of a deoxycholic-calix[4]arene hybrid-type receptor as a chiral stationary phase for HPLC.

We report the synthesis and enantioseparation characteristics of two novel covalently immobilized deoxycholic acid derivatives as chiral stationary phases for high-performance liquid chromatography. In the structure of the first stationary phase, the 3-position of deoxycholic acid is substituted with a 3,5-dinitrophenylcarbamoyl group and the second one has an additional calix[4]arene attached to the carboxylic group of the deoxycholic acid. The chromatographic performance of the stationary phases was evaluated with enantioseparation of N-(3,5-dinitrobenzoyl)-dl-leucine, N-(3,5-dinitrobenzoyl)-dl-valine, omeprazole, diclofop-methyl, dl-mandelic acid and (RS)-pregabalin. Comparison of the performance characteristics of the prepared chiral stationary phases provided evidence for the active involvement of the calix[4]arene unit in the chiral recognition process. Both stationary phases are chemically bonded to the silica and can be used in both normal-phase and reversed-phase modes.

Optically active distorted cyclic triptycenes: chiral stationary phases for HPLC.

A pair of optically active triptycene derivatives ((R,R)- and (S,S)-8) with a distorted cyclic structure were synthesized via an intramolecular etherification and evaluated as a novel chiral selector for high-performance liquid chromatography. The (R,R)- and (S,S)-8-based chiral stationary phases (CSPs) were found to be particularly effective in the resolution of axially chiral biaryl compounds. The importance of the distorted cyclic structure present in 8 for chiral recognition was demonstrated by comparisons with the corresponding non-cyclic model compound ((R,R)-9), which did not display enantioselectivity in the separation of the test racemates.

Ionic liquid-functionalized graphene quantum dot-bonded silica as multi-mode HPLC stationary phase with enhanced selectivity for acid compounds

A novel IL/GQD/SiO2 stationary phase for reversed-phase/normal-phase/ionic exchange and hydrophilic interaction liquid chromatography.

A simple approach to prepare a sulfone-embedded stationary phase for HPLC.

In the present study, a polar-embedded reversed-phase liquid chromatographic stationary phase that contained internal sulfone groups was prepared. The synthesis involved the "thiol-ene" click chemistry between the vinyl functionalized silica and 1-octadecanethiol, followed by the oxidization of sulfide to sulfone groups. The resulting material simultaneously possessed the alkyl chain, i.e. C18, and the internal sulfone groups. Elemental analysis demonstrates that the element contents of the C18/sulfone silica were C 8.94%, H 1.87% and S 0.66%. Chromatographic evaluations indicate that the C18/sulfone stationary phase exhibited a little less retention than the C18/sulfide one. A comparable chromatographic performance of neutral analytes was obtained on these two columns, but much better chromatographic performance in the case of basic and acid analytes was obtained on C18/sulfone stationary phase with additional features such as lower silanol activity, better stability (stable working conditions of pH1.0-10.0), and better compatibility with 100% aqueous mobile phases. The batch-to-batch reproducibility was acceptable (the RSDs of retention times for the probes were no higher than 1.73%), demonstrating the suitability of the applied synthetic strategy for the new stationary phase. The C18/sulfone is a promising polar-embedded RPLC stationary phase.

Preparation and evaluation of a chiral HPLC stationary phase based on cone calix[4]arene functionalized at the upper rim with l-alanine units.

Here we report a new chiral stationary phase (CSP) immobilized on silica gel based on cone calix[4]arene functionalized at the upper rim with two l-alanine units as new chiral selector that has been used in high-performance liquid chromatography. The CSP was prepared by covalently bonding the allyl groups at the lower rim of calix[4]arene to silica gel by thiol-ene click chemistry reaction. Elemental analysis of the CSP showed that 120 μmol of chiral selector bonded per gram of silica gel. 1-Hexene was used for end-capping of unreacted mercapto groups on silica gel. Since the CSP is chemically bonded to the silica, it can be used in the normal-phase and reversed-phase mode and with halogenated solvents as mobile phases, if desired. The chromatographic performance of the CSP was evaluated in the enantioseparation of the 3,5-dinitrobenzoyl derivatives of some amino acids, diclofop-methyl and dl-mandelic acid.

Separation of pharmacologically active nitrogen-containing compounds on silica gels modified with 6,10-ionene, dextran sulfate, and gold nanoparticles

New stationary phases for HPLC are obtained via layer-by-layer deposition of polyelectrolytes and studied: (1) silica gel modified layer-by-layer with 6,10-ionene and dextran sulfate (Sorbent 1); (2) silica gel twice subjected to the above modification (Sorbent 2); and (3) silica gel modified with 6,10-ionene, gold nanoparticles, and dextran sulfate (Sorbent 3). The effect the content of the organic solvent in the mobile phase and the concentration and pH of the buffer solution have on the chromatographic behavior of several pharmacologically active nitrogen-containing compounds is studied. The sorbents are stable during the process and allow the effective separation of beta-blockers, calcium channel blockers, alpha-agonists, and antihistamines. A mixture of caffeine, nadolol, tetrahydrozoline, pindolol, orphenadrine, doxylamine, carbinoxamine, and chlorphenamine is separated in 6.5 min on the silica gel modified with 6,10-ionene, gold nanoparticles, and dextran sulfate.

HPLC Characterization of the Association Mechanism of Organic Compounds with β Cyclodextrin Using a Novel Boron Nitride Nanotube Particulate Stationary Phase

In this paper, a simple homogeneous coating of silica spherical particles with pristine boron nitride nanotubes (BNNTs) was described. BNNTs dissolved in dimethylacetamide (DMAc) were mixed with amino-functionalized silica particles having a 5 μm diameter. Favorable interaction between the amino group and the BNNT surfaces induces the absorption of the BNNTs on the silica. The BNNT-coated silica particles were used as stationary phase for HPLC. For the first time, it was demonstrated that this new particulate BNNT stationary phase can be used for the study of the complexation of solute molecules (terpene molecules used as test drugs in this work) with β cyclodextrin (βCD). The apparent formation constants Kf of terpene derivative/βCD were in the same magnitude as those reported in the literature. The plot of Kf versus the water fraction in the methanol/water mobile phase showed that the BNNT surface played an active role in the complex formation due to terpene/BNNT-specific polar interactions. This work demonstrated that our novel particulate BNNT HPLC stationary phase was an efficient tool to study molecular recognition mechanism and more specifically the association between a drug substance and a target molecule with the aim of reaching biopharmaceutic and clinical applications.

Preparation, characterization, and performance evaluation of UiO-66 analogues as stationary phase in HPLC for the separation of substituted benzenes and polycyclic aromatic hydrocarbons.

UiO-66 analogues are good candidates as stationary phase in HPLC because of their chemical/thermal stability, large surface area, and two cage structures. Here, two UiO-66 analogues, UiO-66-NH2 and UiO-67, were synthesized and used as stationary phase in HPLC to evaluate their performance in the separation of substituted benzenes (SBs) and polycyclic aromatic hydrocarbons (PAHs). The results showed that SBs could be well separated on UiO-66-NH2 column but not on UiO-67 column. Nonetheless, PAHs could be well separated on UiO-67 column. The separation mechanisms of SBs and PAHs on UiO-66 analogues may be involved in the pore size and functional group in the frameworks of UiO-66 analogues. Introduction of the–NH2 into UiO-66 significantly reduced its adsorption capacity for SB congeners, which resulted in less separation of SBs on UiO-66-NH2. As for the separation of PAHs on UiO-67 column, the π-π stacking effect was supposed to play a vital role.

In Situ Growth of Covalent Organic Framework Shells on Silica Microspheres for Application in Liquid Chromatography.

A facile, in situ growth strategy for the synthesis of monodispersed COF@SiO2 microspheres is reported. The microspheres have uniform and controllable COF shells, and are used as the stationary phase for HPLC. The TpBD COF, constructed from 1,3,5-triformylphloroglucinol (Tp) and benzidine (BD), is taken as the COF shell, and aminosilica (SiO2 -NH2 ) is employed as the core to support the TpBD shell. The TpBD shell thickness is adjusted by controlling the concentrations of the Tp and BD monomers. The TpBD@SiO2 packed columns show excellent hydrophobic selectivity, and good reproducibility for the separation of neutral (toluene and ethylbenzene, polycyclic aromatic hydrocarbons), acidic (hydroquinone, p-cresol, and p-chlorophenol), and basic molecules (nucleobases, nucleosides, and deoxynucleosides).

Immobilized strychnine as a new chiral stationary phase for HPLC.

A new ion-exchanger type chiral stationary phase for high-performance liquid chromatography was prepared. The synthetic protocol is based on derivatization of silica with (3-iodopropyl)trimethoxysilane in the first step followed by immobilization of strychnine via quaternization of nitrogen atom of the alkaloid strychnine. The synthesized chiral stationary phase was chromatographically characterized. The main effort was headed towards the evaluation of the enantioselectivity of the novel sorbent. For that purpose a set of suitable chiral probes, specifically, binaphthyl derivatives, was employed. The influence of methanol content, concentration of aqueous ammonium acetate buffer, and its pH on retention factors, separation selectivity, and resolution of the atropoisomers of the mentioned chiral solutes was studied in detail. It was demonstrated that the new chiral stationary phase was capable to separate atropoisomers of four out of seven testing compounds. Despite the strong influence of the above mentioned variables on retention, their impact on selectivity and resolution was rather moderate. Concerning retention mechanism, it seems that electrostatic interaction between the positively charged quaternary nitrogen of the chiral stationary phase and anionic solute participates significantly in the retention process.

Laboratory-Scale Preparative Enantioseparations of Pharmaceutically Relevant Compounds on Commercially Available Chiral Stationary Phases for HPLC.

In response to the outburst of research in the field of synthetic medicinal chemistry, enantioselective chromatography methods based on the use of chiral stationary phases (CSPs) found immediate acceptance as the elective choice for the analytical determinations of the enantiomeric purity of synthetic compounds. In contrast to an initial scepticism, also the preparative-scale applications are gaining increasing recognition as a powerful alternative to enantioselective synthesis for the supply of pure enantiomers of bioactive compounds. The increasing success of liquid chromatography methods has been made possible thanks to the development of highly efficient CSPs allowing the enantioresolution of practically all the chemical classes of chiral compounds. However, only few CSPs are really suitable for preparative- scale applications, being the loading capacity is the major concern for preparativescale enantioseparations. The cellulose- and amylose-based CSPs present the highest loading capacity and enantiodiscrimination power, which makes these CSPs the most versatile and applicable for preparative-scale applications in all the applicable elution modes (reversedphase, normal-phase, and with polar-organic or polar-ionic eluents). However, also other types of CSPs have been successfully employed at this regard (brush-type phases, polyacrylamide and cross-linked di-allyltartardiamide phases as well as cyclodextrin, and glycopeptide containing phases). Several instrumental methods exist for the determination of the absolute configuration of organic compounds in absence of known enantiopure reference standards. The most widely known are X-ray crystallography, followed by chirooptical methods [e.g., electronic and vibrational circular dichroism (ECD and VCD, respectively)] and nuclear magnetic resonance (NMR) spectroscopy. All these aspects will be treated in the review.

Polarizability Effects Dominate the Chromatographic Retention Behavior of Spheroidal and Elipsoidal Metallofullerene Nanospheres

The chromatographic retention behavior of spherical and elipsodial metallofullerenes provides a unique class for studying subtle intermolecular dispersive (London effect) and inductive (Debye effect) solution-state/solid-phase interactions. The known trimetallic nitride endohedral metallofullerene A3N@C80 isomers are nearly spherical A3N@C80-Ih and ellipsoidal A3N@C80-D5h. These metallofullerene isomers are readily available with group IIIB and lanthanide trimetallic nitride clusters (A3N)6+. In the current study, chromatographic HPLC retention behavior is monitored for two different HPLC stationary phases, pentabromobenzyl and pyrenylethyl and augmented by density functional theory computational results. Although dipole moments, lanthanide contraction, and charge transfer from the internal cluster (A3N)6+ are important factors controlling chromatographic retention, our results suggest that the fullerene cage polarizability is the dominant factor controlling chromatographic separation of A3N@C80-Ih and el...

Preparation of porous hollow silica spheres via a layer-by-layer process and the chromatographic performance

Hollow silica spheres possessing excellent mechanical properties were successfully prepared through a layer-by-layer process using uniform polystyrene (PS) latex fabricated by dispersion polymerization as template. The formation of hollow SiO2 micro-spheres, structures and properties were observed in detail by zeta potential, SEM, TEM, FTIR, TGA and nitrogen sorption porosimetry. The results indicated that the hollow spheres were uniform with particle diameter of 1.6 μm and shell thickness of 150 nm. The surface area was 511 m2/g and the pore diameter was 8.36 nm. A new stationary phase for HPLC was obtained by using C18-derivatized hollow SiO2 micro-spheres as packing materials and the chromatographic properties were evaluated for the separation of some regular small molecules. The packed column showed low column pressure, high values of efficiency (up to about 43 000 plates/m) and appropriate asymmetry factors.

Chiral Recognition Ability of an Optically Active Poly(diphenylacetylene) as a Chiral Stationary Phase for HPLC

An optically active poly(diphenylacetylene) with a pendant amide functional group was synthesized by a macromolecular reaction of the optically inactive poly(diphenylacetylene) bearing carboxy grou...