Influence of intermolecular interaction with the eluent on the retention and selectivity in liquid chromatography

Summary The influence of substance — eluent (water-isopropanol mixture) intermolecular interaction on the retention and selectivity of separation in liquid chromatography on silica gel with silanized surface has been investigated for benzene and toluene derivatives. The interaction greatly depends on the nature of the polar functional groups, their position in the benzene ring and the existence of intramolecular interaction.     

Selectivity of liquid-adsorption chromatography on hydroxylated silica gel with nonpolar and polar eluents

Summary The effect of nonpolar (hexane, decane, benzene) and polar (water, isopropanol, water+isopropanol) eluents on separation of aromatic hydrocarbons and their derivatives in liquid-adsorption chromatography on hydroxylated silica gel columns has been studied. The work has revealed that the traditional application areas of hydroxylated silica gel in liquid chromatography may be extended. In particular it has been shown that, first, polar compounds may be separated on hydroxylated silica gel with nonpolar eluents at high temperatures (100–150°C) and that polar and nonpolar compounds may be separated using pure water as eluent. The effect of adsorbed moisture on retention behaviour of silica gel with nonpolar eluents has also been investigated.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Comparison of retention on traditional alkyl, polar endcapped, and polar embedded group stationary phases

The development of new RP stationary phases containing polar groups has provided the chromatographer with a variety of stationary phase choices with differing selectivities. Polar endcapped and polar embedded group stationary phases have found use in solving a wide variety of separation problems, especially for the efficient separation of organic bases as well as separations necessitating the use of highly aqueous mobile phases. In this report, the retention thermodynamics of small, nonpolar solutes on traditional alkyl, polar endcapped, and polar embedded group stationary phases are compared. It is found that the nonpolar (methylene) transfer enthalpy is less favorable when polar embedded group phases are used, when compared to traditional or polar endcapped phases. In contrast, the transfer enthalpy of a phenyl group is found to be more favorable when a polar endcapped phase is used. In addition, the retention characteristics of these phases are compared using a set of solutes with differing solvatochromic parameters. Hydrogen-bond acids appear to have enhanced retention on polar embedded group phases, while hydrogen-bond bases have enhanced retention on polar endcapped phases.     

Influence of intermolecular interaction with the eluent on the retention of phenol and aniline on polar and non-polar surfaces

Summary The retention order of aniline and phenol on hydroxylated silica gel surface is reversed with the increase of the concentration of a polar component in the eluent. At minor (about 1%) concentrations of isopropanol in hexane aniline emerges first followed by phenol, the elution order being reversed with the increase of isopropanol concentration above 2%. The same behaviour is observed for silica gel with chemically bonded C₁₆ n-alkyl groups and for porous styrene-divinylbenzene copolymer. In all these cases the retention depends to a great extent on substance-eluent intermolecular interactions. At high isopropanol concentration in hexane the rise of column temperature changes the retention order of aniline and phenol on silica gel with hydroxylated surface since the association of these molecules with isopropanol as well as the isopropanol adsorption weaken as the temperature increases.     

Regularities in the retention of isomeric aromatic hydrocarbons in liquid chromatography II. Analysis of polymethyl- and monoalkylbenzenes on silanized silica gel

Summary The regularities of the retention of polymethyl- and monoalkylbenzenes on a nonpolar adsorbent (silanized silica gel) with a polar eluent (23 isopropanol-water) have been studied. In contrast to the retention of the same compounds on a polar adsorbent (silica gel with hydroxylated surface) and with a nonpolar eluent (hexane) polymethylbenzenes are retained on silanized silica gel for a shorter time than the corresponding monoalkylbenzene isomers. The retention order of tert.-, sec.- and n-butylbenzenes is the reverse of that observed on silica gel having a hydroxylated surface. The retention order of xylenes, trimethyl- and tetramethylbenzenes is also the reverse of their retention order on silica gel having a hydroxylated surface. All the mixtures of the corresponding homologues and isomers have been separated.     

Investigation of the role of adsorption at the stationary phase interface in capillary columns prepared with cross-linked phases

Summary On the basis of the adsorption-absorption additivity theory the influence of adsorption on the retention of polar samples has been quantitatively studied using fused-silica capillary columns coated with nonpolar cross-linked and non-cross-linked liquid stationary phases. It is shown that cross-linking of a nonpolar stationary phase increases the contribution of adsorption to the retention of polar compoments. As a result the retention of polar compounds increases on crosslinked stationary phases as compared with the initial (non cross-linked) phase. “The material of this paper was presented at the 15th International Symposium on Chromatography, Nürnberg, October, 1984”     

Preparation and evaluation of diblock copolymer‐grafted silica by sequential surface initiated‐atom transfer radical polymerization for reverse‐phase/ion‐exchange mixed‐mode chromatography

A novel approach that involved the grafting of diblock copolymer with two types of monomer onto substrate by sequential surface initiated‐atom transfer radical polymerization was proposed to prepare a mixed‐mode chromatographic stationary phase. The distinguishing feature of this method is that it can be applied in the preparation of various mixed‐mode stationary phases. In this study, a new reverse‐phase/ion‐exchange stationary phase was prepared by grafting hydrophobic styrene and cationic sodium 4‐styrenesulfonate by the proposed approach onto silica surface. The chromatographic properties of the prepared stationary phase were evaluated by the separation of benzene derivatives, anilines, and β‐agonists, and by the effect of pH values and acetonitrile content on the retention. Compared with typical RP columns, the prepared stationary phase achieved the better resolution and higher selectivity at a shorter separation time and lower organic content. Moreover, the application of the prepared column was proved by separating widely distributed polar and charged compounds simultaneously.     

Evaluation of Inclusion Selectivity of (2-hydroxy-3-methacryloyloxypropyl β-cyclodextrin-co-N-vinylpyrrolidone) Copolymers Coated Silica Stationary Phase by High Performance Liquid Chromatography

A comparative study of the retention behaviour of disubstituted benzene derivatives on (2-hydroxy-3-methacryloyloxypropyl -cyclodextrin-co-N-vinylpyrrolidone) copolymers physically adsorbed onto porous silca gel was achieved. Under reversed-phase mode, the separation process is based on an inclusion complex formation, and the inclusion selectivity is strongly influenced by hydrogen bonds and/or steric effects. The influence of cyclodextrin derivatives used as mobile phase additives for the conventional reversed-phase high-performance liquid chromatography was also examined with the aim to confirm the formation of inclusion complexes between CD derivatives and test molecules. Under normal-phase mode, it was found that the retention and separation processes are mainly controlled by hydrophilic interactions between the polar substituents of the solute and the hydroxyl groups of the cyclodextrin units. Finally, the enantiomer separation ability was briefly demonstrated.     

Sorption Characteristics of Porous Styrene-Divinylbenzene Copolymers Filled with Modified Silica

The structural parameters of porous styrene-divinylbenzene copolymer, unfilled and filled with silica containing surface trimethylsilyl and silicon hydride groups were studied by aniline and p-chloroaniline adsorption. It has been shown that embedding of chemically modified silica affects the material porosity and decreases the copolymer swelling in benzene.     

Control of adsorption and solubility in gradient high performance liquid chromatography 1. Principles of sudden transition gradients and elution characteristics of copolymers from styrene and methacrylates

Summary Proper retention of polymers in high performance liquid chromatography often requires injection into a starting eluent which is not a solvent for the sample under investigation. In this case, the polymer is precipitated at the top of the column. Subsequent gradient elution has to be performed by addition of an eluent with sufficient chromatographic strength and solvent power. In normal phase chromatography, it must be a solvent of high polarity. With the gradient elutions reported so far, polarity and dissolution power were simultaneously increased.The present paper reports the separate control of solvent strength and chromatographic power by applying gradient programs which include sudden addition of a moderately polar solvent. The amount of the latter does not suffice for elution, which is performed by subsequent, controlled addition of a highly polar nonsolvent. Sudden transition gradients of this kind work with, e.g.,iso-octane as a nonpolar starting eluent, tetrahydrofuran as a solvent of intermediate polarity, and methanol as a strongly polar nonsolvent. They have been applied to copolymers from styrene and ethyl methacrylate, methyl methacrylate, or methoxyethyl methacrylate.     

Structure and supramolecular structures of star-shaped fullerene-containing heteroarm polymers in deuterotoluene

Self-organization of star-shaped polymers containing six PS arms and six polar polymer arms on a common C₆₀ branching center is studied by means of small-angle neutron scattering in deuterotoluene. The results are compared with the corresponding characteristics of six-arm star-shaped fullerene-containing PSs. It is shown that the incorporation of additional polar arms into a six-arm macromolecule leads to its compression due to an increase in the degree of coiling of polar chains in the nonpolar solvent. In solution, heteroarm stars give rise to supramolecular structures in the form of clusters whose dimensions and density depend on the nature of the polar arms. Stars containing PS and poly(2-vinylpyridine) arms are weakly associated, and the mean number of particles in an associate is ∼1.3. Hybrid polymers containing PS and poly(tert-butyl methacrylate) arms demonstrate capability for mutual penetration that favors the appearance of large structures that have a diameter of ∼50 nm and that include up to 12 macromolecules. Hybrid stars containing PS and diblock copolymer (poly(2-vinylpyridine)-poly(tert-butyl methacrylate)) arms exhibit moderate self-organization that manifests itself in the formation of chain associates built from four macromolecules.     

Naphthyl methacrylate‐based monolithic column for RP‐CEC via hydrophobic and π interactions

A neutral naphthyl methacrylate‐based monolith (NMM) was introduced for RP‐CEC of various aromatic compounds via hydrophobic and π interactions. It was characterized over a wide range of elution conditions to gain insight into its RP retention mechanism toward the various solute probes under investigation. First, the NMM column exhibited cathodal EOF at various mobile phase compositions and pH suggesting that although the NMM column is void of fixed charges, it acquires a negative zeta potential. It is believed that the negative zeta potential is imparted by the adsorption of mobile phase ions to the NMM surface. The NMM column exhibited π–π interactions in addition to hydrophobic interactions due to the aromatic and nonpolar nature of its naphthyl ligands. In all cases, the retention of the various aromatic test solutes including PAHs, benzene derivatives, toluene derivatives, anilines and toluidine, tolunitrile and nitrotoluene positional isomers on the NMM column were compared to their retention on an octadecyl acrylate‐based monolithic column. Not only were the values of the retention factors of the various solutes on the NMM column higher than those obtained on the octadecyl acrylate‐based monolithic column under otherwise the same CEC conditions, but the elution orders were also different on both columns with a superior and unique selectivity exhibited by the NMM column.     

Imidazolium‐embedded iodoacetamide‐functionalized silica‐based stationary phase for hydrophilic interaction/reversed‐phase mixed‐mode chromatography

A novel imidazolium‐embedded iodoacetamide‐functionalized silica‐based stationary phase has been prepared by surface radical chain‐transfer polymerization. The stationary phase was characterized by Fourier transform infrared spectrometry, thermogravimetric analysis, and element analysis. Fast and efficient separations of polar analytes, such as nucleosides and nucleic acid bases, water‐soluble vitamins and saponins, were well achieved in hydrophilic interaction chromatography mode. Additionally, a mixed mode of hydrophilic interaction and reversed‐phase could be also obtained in the analysis of polar and nonpolar compounds, including weak acidic phenols, basic anilines and positional isomers, with high resolution and molecular‐planarity selectivity, outperforming the commercially available amino column. Moreover, simultaneous separation of polar and nonpolar compounds was also achieved. In conclusion, the multimodal retention capabilities of the imidazolium‐embedded iodoacetamide‐functionalized silica‐based column could offer a wide range of retention behavior and flexible selectivity toward hydrophilic and hydrophobic compounds.     

PoraPLOT Q: A porous layer open tubular column coated with styrene-divinylbenzene copolymer

A porous polymer is deposited on the inner wall of fused silica capillary columns. The retention characteristics of this porous polymer were evaluated and found to be comparable with Porapak Q. The porous polymer has a high retention volume which enables the separation of permanent gases at ambient temperatures or higher. The hydrophobic character of the porous polymer allows the injection of water containing samples without changing retention due to adsorption of water. The inertness of the porous polymer allows the elution of a range of apolar and polar compounds. The maximum temperature of the porous polymer was estimated to be 250°C. With this new type of capillary column, high resolution separations are obtained in combination with short analysis times.     

The interaction of monosubstituted benzenes with the stationary liquid in gas liquid chromatography

In gas liquid chromatography (GLC), the relative retention values log gamma was mainly expressed by van der Waals energy (the sum of the dispersion E(dis) and repulsive E(rep) energies) to the interactions between monosubstituted benzene derivatives and the nonpolar stationary liquid as squalane. The single exception was that of anilines, and it was corrected by the electrostatic energy (E(ES)) due to C-H/pi hydrogen bond. When the stationary liquid changed from the nonpolar to polar, log gamma was estimated by the inductive interaction energy (included in E(ES)) in addition to the sum of E(dis) and E(rep). In the benzene solution, the relative equilibrium values log K/K(o) introduced from the interactions between phenol and substituted benzene derivatives were estimated by E(ES). The E(ES) of COCH(3), CO(2)C(2)H(5) groups is especially originated in the excited dipole moments micro(e). The relative frequency values log nu/nu(o) derived from O-H or O-D stretching vibration of phenol or methanol-D gave the correlation to E(ES) as well as log K/K(o). That of anilines-methanol-D however had been out of a linear relation to E(ES). The cause is concluded that the aniline-methanol-D is making the proton transfer structure from the discussion about the proton affinity (PA) of the base.     

Grafting by in situ coupling of epoxy groups of a living copolymer with an anionic living polymer

A tetrahydrofuran (THF) solution of the living random copolymer of methyl methacrylate (MMA) and glycidyl methacrylate (GMA) was prepared by the living anionic copolymerization of the two monomers, using 1,1‐diphenylhexyllithium (DPHLi) as initiator, in the presence of LiCl ([LiCl]/[DPHLi]₀ = 3), at −50°C. The copolymer thus obtained has a controlled composition and molecular weight and a narrow molecular weight distribution. By introduction of an anionic living polystyrene (poly(St)) or anionic living polyisoprene (poly(Is)) solution into the above system at −30°C, a coupling reaction took place and a graft copolymer with a polar backbone and nonpolar side chains was produced. The solvent used in the preparation of the living poly(St) or poly(Is) affects the coupling reaction. When benzene was the solvent, a graft copolymer of high purity, controlled graft number and molecular weight, and narrow molecular weight distribution (M_w/M_n = 1.11–1.21) was obtained. In the coupling reaction, the living poly(St) reacted only with the epoxy groups and not with the carbonyls of the backbone polymer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 105–112, 1999     

Gradient high performance liquid chromatography of block copolymers of styrene andt-butyl methacrylate II. Association phenomena in mixtures of block copolymer with polystyrene

Summary Block copolymers of styrene andt-butyl methacrylate can be analysed by methanol/tetrahydrofuran gradients on C18 or phenyl bonded phase columns. On both of these columns, retention increases with styrene content of the samples. At 50°C, the retention of PS or a block copolymer containing 45% styrene was longer on the phenyl than the C18 columns. This indicates the contribution of adsorption to retention on phenyl bonded phase columns. Lowering the temperature from 50 to 30°C caused earlier elution of part of the sample from the phenyl phase. On a C18 phase the same drop in temperature improved the shape of the peak, which also started later than at 50°C. This effect of temperature is generally observed in polymer retention due to an adsorption mechanism, whereas increasing retention with decrease in temperature is characteristic of a precipitation mechanism.The block copolymer investigated contained 15% free polystyrene precursor which could not be separated from the block copolymer under the conditions employed. The addition of 20% PS homopolymer with a molecular weight similar to that of the styrene block in the copolymer showed that the polystyrene eluted together with the block copolymer, whereas the addition of PS homopolymer with a much higher molecular weight caused an extra peak at the expected elution time.Part I see Ref. [1].Dedicated to Professor Leslie S. Ettre on the occasion of his 70th birthday.     

Factors influencing retention and resolution of substituted alkylbenzenes in reversed-phase liquid chromatography

Summary The retention data of isomeric xylenes, ethyltoluenes and diethylbenzenes, and of mesitylene, benzene, toluene and ethylbenzene were obtained on a reversedphase column using methanol-water and ethanol-water mobile phases at four different temperatures. This database was used to relate the dependence of solute retention and resolution on the polarity of the mobile phase, solute dipole moment, and column temperature. The additivity of the free energy of the transfer of solute molecules or solute segments from the stationary phase to the mobile phase, was examined for the isomeric compounds. For this, the logarithm of the net retention volume was substituted for the free energy. Deviations from the additivity of free energies indicate that the separation of isomeric substituted alkylbenzenes is governed by their differential interactions with both the polar mobile phase and nonpolar stationary phase. Among the disubstituted alkylbenzenes,ortho-isomers favor the mobile phase more andpara-isomers tend to prefer the stationary phase more. Themeta-isomers are found to follow the additivity rule closely. These trends are amplified as the polarity of the mobile phase is increased indicating that these isomers are resolved better in water-rich mobile phases. These findings are substantiated by analogous results from gas-liquid chromatographic retention data, estimation of dipole moment effects, and examination of the entropic and enthalpic contributions to the net retention volume.Dedicated to Professor Leslie S. Ettre on the occasion of his 70th birthday.     

芳硫基乙酸酯及其氧化产物的色谱行为(Ⅲ)──在反相高效液相色谱中的行为

芳硫基乙酸酯及其氧化产物的色谱行为（Ⅲ）──在反相高效液相色谱中的行为练鸿振,茅力,苗进,徐小青,张正（南京大学现代分析中心,化学系,南京,２１００９３）关键词芳硫基乙酸酯;芳亚磺酰基乙酸酯;芳磺酰基乙酸酯;反相高效液相色谱在现代有机合成中,含硫有机...     

十八烷基改性纳米二氧化硅涂层毛细管柱在毛细管电色谱中的应用

采用液相沉积技术制备了纳米二氧化硅涂层毛细管,经十八烷基改性,将其作为开管毛细管电色谱(OTCEC)分离介质。研究了该涂层毛细管的电渗流行为,考察了烷基苯和多环芳烃的毛细管电色谱分离性能。结果表明,该涂层固定相对这些化合物表现出较强的疏水作用;增加液相沉积涂层次数有利于增加溶质的保留因子,四种多环芳烃和四种苯同系物在该柱上可实现基线分离。此外,该涂层制备简单、重现性好,并在应用中表现出较高的稳定性。