Polypyrrole-coated silica as a new stationary phase for liquid chromatography

Summary Polypyrrole chloride and polypyrrole dodecylsulfate coated-silica packing materials have been synthesized. Reverse-phase chromtographuy was employed to characterise both packings. A series of test compounds with known properties was used as molecular probes. They included benzene and derivatives, basic drugs, and polyaromatic hydrocarbons. A commericial C₁₈ column was also used for the purpose of comparison in some cases.     

Ionic liquid-modified silica as a new stationary phase for chromatographic separation

A new stationary phase based on silica modified with 1-methyl-3-propylimidazolium chloride was synthesized and characterized in this paper. A derivative of 1-methyl-3-propylimidazolium chloride was used to chemically modify the surface of silica particles to act as the stationary phase for HPLC. The modified particles were characterized by Fourier Transform Infrared (FT-IR), ¹³C NMR spectroscopy and thermogravimetric analysis (TGA). The surface modification procedure rendered particles with a surface coverage of 0.89 μmol/m² of alkylimidazolium chloride. Columns packed with the modified silica and blank silica particles were tested under HPLC conditions. Preliminary evaluation of the stationary phase for HPLC was performed using aromatic compounds as model compounds. The separation mechanism appears to involve multiple interactions including ion exchange, hydrophobic and electrostatic interactions.     

Conalbumin-conjugated silica gel, a new chiral stationary phase for high-performance liquid chromatography.

A new chiral stationary phase using conalbumin (from chicken egg white) was developed for high-performance liquid chromatography. Chiral resolution of racemic azelastine, an antiallergic drug, was achieved on a conalbumin-conjugated silica gel column. The effects of the pH, the concentration of organic solvents and salts in the mobile phase, and the temperature on the capacity factor and resolution of racemic azelastine were examined. This column shows good stability and can separate optical isomers with an aqueous mobile phase. It should be very useful in studies on pharmacokinetics and in clinical chemistry.     

Microdispersed sintered nanodiamonds as a new stationary phase for high-performance liquid chromatography

The microdispersed sintered nanodiamonds are evaluated as a new prospective stationary phase for normal-phase high-performance liquid chromatography.     

Preparation and evaluation of a novel bonded imidazolium ionic liquid as stationary phase for gas chromatography

1‐Butyl‐3‐[(3‐trimethoxysilyl)propyl]imidazolium chloride ionic liquid was synthesized and chemically modified onto the inner wall of a fused capillary column as a stationary phase for gas chromatography. The 1‐butyl‐3‐[(3‐trimethoxysilyl)propyl]imidazolium chloride ionic liquid bonded capillary column was evaluated in detail. The results revealed that the ionic liquid bonded capillary column exhibited high column efficiency of 1.08 × 10⁴ plates/m, and good chromatographic separation selectivity (α ) for polar and non‐polar substances, and a good thermal stability between room temperature and 400°C. Moreover, the determination of thermodynamic parameters and the linear solvation energy relationship were further carried out. The results indicated that the chromatographic retention of each probe molecule on the ionic liquid bonded stationary phase was an enthalpy‐driven process, and the system constants of the linear solvation energy relationship signified that the dispersion interaction, the hydrogen bonding acidity and hydrogen bonding basicity were dominant interactions between probes and stationary phase among five interactions during the chromatographic separation. However, the contribution of each specific interaction for the stationary phase is ranked as the dispersion interaction > the hydrogen bonding basicity > the hydrogen bonding acidity.     

Layer-by-layer self-assembled multi-walled carbon nanotubes/silica microsphere composites as stationary phase for high-performance liquid chromatography

Multi-walled carbon nanotubes (MWCNTs) were layer-by-layer assembled onto silica microspheres to form MWCNTs/SiO(2) composites and were characterized by surface analysis, elemental analysis, and contact angle. The composite was used as a stationary phase in HPLC for the separation of many kinds of aromatic compounds. The separation of polycyclic aromatic hydrocarbons (PAHs) affected by the number of MWCNTs layers on SiO(2) was investigated. Retention times and resolutions of PAHs were affected by the assembled layer of MWCNTs and the type of organic additive in the mobile phase. When the MWCNTs layer increased to 5 (MWCNTs/SiO(2)-5), PAHs can be completely separated. Aromatic compounds with different substituents can be well separated when only water was used as the eluent on the MWCNTs/SiO(2)-5 column. Decreasing the pH of the eluent can increase the retention factors of organic acids. Organic amines can also be separated with acetonitrile as organic additive, which were eluted in the order of the electronic cloud density of their aromatic rings. Comparing the MWCNTs/SiO(2)-5 column with a commercial HPLC column, it was clearly shown that the commercial column exhibited the characteristic of hydrophobicity, and the MWNCTs/SiO(2)-5 column exhibited the characteristic of a large π-electron system.     

N-Methylimidazolium anion-exchange stationary phase for high-performance liquid chromatography

In this paper, the preparation of a new anion-exchange phase based on N-methylimidazolium immobilized on silica is described. HPLC separations of common inorganic anions, including an iodate, chloride, bromide, nitrate, iodide, and thiocyanate, were performed using a HPLC column (200 x 4.6mm I.D.) packed with the said phase, and phosphate buffer solution and acetate buffer solution as the mobile phases respectively, with UV detection at 200 nm. The effects of pH and the concentration of the eluent on the separation of anions were studied. With the efficiency and resolution of the column calculated, the results showed that this new phase can be used in the analysis of these in organic anions with great prospects. At the same time, successful separations of some organic anions, amines and nucleotides have also been obtained respectively using this new phase. The phase displayed a main strong anion-exchange mechanism and a coexistent reverse-phase interaction, etc.     

Novel imidazolium stationary phase for high-performance liquid chromatography

A new imidazolium anion-exchange phase immobilized on silica is synthesized. HPLC separations of common inorganic anions (IO3-, Cl-, NO2-, Br-, NO3-, I-, SCN-) have been performed using a HPLC column (200 mm x 4.6 mm I.D.) packed with this stationary phase, with a phosphate buffer solution as the mobile phase and UV detection at 200 nm. The effects of pH and concentration of eluent on the separation of anions have been studied. Chromatographic parameters are calculated and the results show that the new stationary phase is of significant potential for the analysis of these anions. Successful separations of some ordinary organic anions have also been achieved with the said stationary phase. Meaningfully, organic and inorganic anions can be determined simultaneously and satisfactorily with several neutral compounds using the column. The separation of some organic compounds including hydroxybenzenes, bases and amines by this stationary phase with only water as the eluent has been investigated.     

Polysiloxane-encapsulated stationary phase for reversed-phase high-performance liquid chromatography

Summary Silica beads of 6-μm average diameter were silanized with methylvinyldiethoxysilane and then subjected to encapsulation with poly(methylvinylsiloxane). The resulting product is a new stationary phase for reversed-phase high performance liquid chromatography (RP-HPLC) which has superior ability for the separation of polar, non-polar and basic compounds. The chromatographic peaks are symmetric. Its stability has been studied; after continuous use for three months the carbon content and chromatographic behaviour of the phase were unchanged. on to the silica surface to given an uniform organic film. Material prepared in this way has both good chromatographic behaviour and superior selectivity. Because contact of the silica matrix with the mobile phase is avoided, the alkali-resisting ability of the stationary phase is increased. The non-specific adsorption of alkaline solutes on to the silica surface is also avoided because of the complete coverage of surface silanol groups. Reports of stationary phases encapsulated with polystyrene [6], polybutadiene [I] and octadecylsiloxane polymers have recently appeared in the literature [3]. In this paper we report the encapsulation of poly-(methylvinylsiloxane) (analogous to the phase SE-31 often used in GC) on to a silica matrix previously modified with methylvinyldiethoxysilane. The resulting phase has superior performance in reversed-phase HPLC.     

新型吡咯烷键合反相高效液相色谱固定相的制备与研究（英文）

正A new ionic liquid-based high-performance liquid chromatography stationary phase is reported.A derivative of N-methyl pyrrolidinium tetrafluoroborate was covalently immobilized on the surface of silica particles to prepare silica-based N-methyl pyrrolidinium tetrafluoroborate(SilprMP BF4)stationary phase.The obtained ionic liquid-modified silica was evaluated and confirmed by elemental analysis,infrared spectroscopy,and thermogravimetric analysis.A column was packed with the modified particles.The retention behavior of aromatic compounds,alkyl benzenes,and acidic and basic compounds on the SilprMP BF4 stationary phase was studied under reversed-phase liquid chromatography conditions.The effect of the eluent pH on the separation of the acidic and basic compounds was also studied.The new stationary phase involves multiple retention mechanisms,such as electrostatic,hydrophobic,ion-dipole,and anion-exchange interactions,which might lead to multipurpose separation media.     

Microwave-immobilized polybutadiene stationary phase for reversed-phase high-performance liquid chromatography

Polybutadiene (PBD) has been immobilized on high-performance liquid chromatography (HPLC) silica by microwave radiation at various power levels (52-663 W) and actuation times (3-60 min). Columns prepared from these reversed-phase HPLC materials, as well as from similar non-irradiated materials, were tested with standard sample mixtures and characterized by elemental analysis (%C) and infrared spectroscopy. A microwave irradiation of 20 min at 663 W gives a layer of immobilized PBD that presented good performance. Longer irradiation times give thicker immobilized layers having less favorable chromatographic properties.     

Characterization of a novel pyridinium bromide surface confined ionic liquid stationary phase for high-performance liquid chromatography under normal phase conditions via linear solvation energy relationships

Utilizing linear solvation free energy relationship methodology, a novel pyridinium bromide surface confined ionic liquid (SCIL) stationary phase was characterized under normal phase high-performance liquid chromatographic conditions. A limited set of neutral aromatic probe solutes were utilized to rapidly assess the utility of the LSER model, using mobile phases of hexane modified with 2-propanol. The excellent correlation of the global fit across the mobile phase composition range used in this study for the experimental and calculated retention values (R(2)=0.994) indicates that the LSER model is an appropriate model of characterizing this polar bonded phase under normal phase conditions. For a limited subset of compounds, retention on the pyridinium bromide SCIL stationary phase is more highly correlated with that obtained on a cyano column than on a diol column under NP conditions.     

Anion separations for liquid chromatography using propylpyridinium silica as the stationary phase

This work describes the characterization and potential applications of a silica-based anion-exchange phase prepared by a two-step modification process that incorporates a propylpyridinium group. The effects of pH and eluent concentration on anion separation were examined using 150 mm × 3.9 mm HPLC columns packed with the new phase. The mobile phase pH values ranged from 3.8 to 6.6 using phthalic acid/Tris solutions. The best separation was achieved using 2.5 mmol L⁻¹ phthalate/2.4 mmol L⁻¹ Tris solution at pH 4.2 as mobile phase with non-suppressed conductivity detection. The new stationary phase was used for the separation of some inorganic and organic anions showing good resolution. The stability of the silica-based anion exchange phase was also evaluated.Analytical curves, for concentrations ranging from 0.25 to 10 mg L⁻¹ for the inorganic anions chloride, nitrite, bromide and nitrate, showed good linear correlations (r > 0.998). The method was tested with certified rainwater samples. The measured and certified values were in good agreement, indicating that the new phase holds significant promise for the analysis of these anions in environmental samples.     

咪唑离子液体键合硅胶固定相纯水洗脱分离碱基、酚类和药物化合物

采用N-甲基咪唑和氯丙基咪唑反应的方法制备得到了离子液体键合硅胶固定相,并利用该固定相中的咪唑环阳离子和被分析物之间存在的多重作用机理如疏水作用、静电吸引和排斥及氢键作用等,以纯水作为流动相,成功地分离了碱基(胞嘧啶、胸腺嘧啶、2-氨基嘧啶和6-氯鸟嘌呤)、酚类化合物(间氨基酚、间苯二酚和间硝基酚)以及3种药物化合物(盐酸吗啉呱、阿昔洛韦和头孢氨苄)。采用没有添加任何有机溶剂和缓冲液的纯水作流动相,既绿色环保,又节约经济,简单方便。对该固定相分离这些化合物的保留机理做了探讨。     

One-pot synthesis of pillar[5]quinone-amine polymer coated silica as stationary phase for high-performance liquid chromatography

To expand the application of pillararene in chromatographic separation, we designed and fabricated a pillar[5]quinone-amine polymer coated silica through quinone-amine reaction by facile one-pot synthesis method, which was applied as a stationary phase for high-performance liquid chromatography. Separation of hydrophobic compounds, hydrophilic compounds, halogenated aromatic compounds, and 11 aromatic positional isomers was achieved successfully in this stationary phase. Reverse-phase separation mode and hydrophilic-interaction separation mode were proved to exist, indicating the potential application of the mix-mode stationary phase. Studies of chromatographic retention behavior and molecular simulation showed that multiple interactions might play an important role in the separation process, including hydrophobic interaction, hydrogen-bonding interaction, aromatic π-π interaction, electron donor-acceptor interaction, and host-guest interaction. Column repeatability and stability were tested, which showed relative standard deviations of retention time less than 0.2% for continuous 11 injections, and the durability relative standard deviations of retention time were less than 0.91% after 90 days. This novel design strategy would broaden the application of pillararene-based covalent organic polymer in chromatography and separation science.     

Homochiral organic molecular cage RCC3-R-modified silica as a new multimodal and multifunctional stationary phase for high-performance liquid chromatography

In this work, homochiral reduced imine cage was covalently bonded to the surface of the silica to prepare a novel high-performance liquid chromatography stationary phase, which was applied for the multiple separation modes such as normal phase, reversed-phase, ion exchange, and hydrophilic interaction chromatography. The successful preparation of the homochiral reduced imine cage bonded silica stationary phase was confirmed by performing a series of methods including X-ray photoelectron spectroscopy, thermogravimetric analysis, and infrared spectroscopy. From the extracted results of the chiral resolution in normal phase and reversed-phase modes, it was demonstrated that seven chiral compounds were successfully separated, among which the resolution of 1-phenylethanol reached the value of 3.97. Moreover, the multifunctional chromatographic performance of the new molecular cage stationary phase was systematically investigated in the modes of reversed-phase, ion exchange, and hydrophilic interaction chromatography for the separation and analysis of a total of 59 compounds in eight classes. This work demonstrated that the homochiral reduced imine cage not only achieved multiseparation modes and multiseparation functions performance with high stability, but also expanded the application of the organic molecular cage in the field of liquid chromatography.     

Immobilized polysiloxanes as stationary phases for high-performance liquid chromatography and solid phase extraction

Polysiloxanes immobilized onto the surfaces of porous silica particles have proven to be good stationary phases for the separation of multiresidues of pesticides and their metabolic/degradation products by reversed-phase high-performance liquid chromatography (RP-HPLC). Similar materials have proven effective for pre-concentration and clean-up procedures using solid phase extraction. The present paper describes the preparation and some applications of several of these packing materials.