Polar Stationary Phases Research Articles

Mathematical Modelling in Analytical Chromatography: Problems and Solutions

Based on an analysis of the results of original research performed in the Laboratory of Sorption Methods of the Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences within the project “Mathematical Chromatograph,” the review covers the aim and strategy of the imitation modeling of high-performance chromatography; associated problems of the theory of intermolecular interactions; classifications of polar stationary phases by their selectivity; descriptions of the kinetics and dynamics of sorption processes, choice of the composition of multicomponent mobile phases in HPLC and ion chromatography using the method of the dynamic map of a chromatographic system; and the development of alternating gradient modes using a mathematical experiment.

Supercritical fluid chromatography for the analysis of natural dyes: From carotenoids to flavonoids.

Plant-derived natural dyes are used in a variety of formulated products, from food to cosmetics and pharmaceutics. In addition to their color, they also provide some bioactivity. While they are mostly analyzed with high-performance liquid chromatography, supercritical fluid chromatography was also employed for several dye families, mostly for carotenoids and chlorophylls, and more recently for anthraquinones and flavonoids. These supercritical fluid chromatography methods are described in this review. Because the dyes have different structures and structural variations (polarity, isomers, etc.), the best chromatographic system to achieve their separation is not always the same. Hydrophobic stationary phases are preferred for the most hydrophobic dyes (chlorophylls and carotenoids) while polar stationary phases are preferred for the polar dyes (anthraquinones and flavonoids). Regarding the mobile phase composition, chlorophylls and carotenoids are best eluted with moderate proportions of co-solvent in CO2 (about 40%), while the most polar glycosylated flavonoids require higher proportions of co-solvent and acidic additives. Because dyes are colorful, ultraviolet-visible detection is often sufficient, while mass spectrometry offers additional structural information. Furthermore, fundamental information can also be gained through chromatographic analysis of dyes: either solubility in supercritical fluids, in view of their extraction, or retention behavior providing an understanding of stationary phase properties.

Relative significance of hydrophilic partitioning and surface adsorption to the retention of polar compounds in hydrophilic interaction chromatography

It is commonly acknowledged that the retention of non-ionized polar analytes on polar stationary phases is governed by hydrophilic partitioning and surface adsorption. However, it has been difficult to evaluate whether partitioning or adsorption is the dominant mechanism for a specific polar compound on a polar stationary phase. We have developed a simple method based on the thermodynamic principle of partitioning to quantitatively investigate the retention contributed by the partitioning or adsorption mechanism. By varying phase ratio through changing salt concentration in the mobile phase, we were able to determine the distribution coefficients of cytosine between the adsorbed water layer and the mobile phase containing various levels of acetonitrile. The retention factors of cytosine attributed to partitioning and adsorption were quantitatively determined. The results demonstrate that the dominant retention mechanism for cytosine is hydrophilic partitioning on ZIC-HILIC, XBridge Amide and LUNA-HILIC columns.

Estimation of the Polarity of Stationary Phases for Gas Chromatography Based on Spectral Parameters

Estimation of the Polarity of Stationary Phases for Gas Chromatography Based on Spectral Parameters

Comparison of the Fitting Performance of Retention Models and Elution Strength Behaviour in Hydrophilic-Interaction and Reversed-Phase Liquid Chromatography

Hydrophilic interaction liquid chromatography (HILIC) is able to separate from polar to highly polar solutes, using similar eluents to those in the reversed-phase mode (RPLC) and a polar stationary phase, where water is adsorbed onto its surface. It is widely accepted that multiple modes of interaction take place in the HILIC environment, which can be far more complex than the interactions in an RPLC column. The behaviour in HILIC should be adequately modelled to predict the retention with optimisation purposes and improve the understanding on retention mechanisms, as is the case for RPLC. In this work, the prediction performance of several retention models is studied for seven HILIC columns (underivatised silica, and silica containing diol, amino and sulfobetaine functional groups, together with three columns recently manufactured with neutral, anionic, and cationic character), using uracil and six polar nucleosides (adenosine, cytidine, guanosine, thymidine, uridine, and xanthosine) as probe compounds. The results in HILIC are compared with those that were offered by the elution of several polar sulphonamides and diuretics analysed with two C18 columns (Chromolith Speed ROD and Zorbax Eclipse XDB). It is shown that eight retention models, which only consider partitioning or both partitioning and adsorption, give similar good accuracy in predictions for both HILIC and RPLC columns. However, the study on the elution strength behaviour, at varying mobile phase composition, reveals similarities (or differences) between RPLC and HILIC columns of diverse nature. The particular behaviour for the HILIC and RPLC columns was also revealed when the retention, in both modes, was fitted to a model that describes the change in the elution strength with the modifier concentration.

Evaluation of gas chromatography for the separation of a broad range of isotopic compounds

The separation of deuterated compounds from their protiated counterparts is essential in areas of drug discovery and development, investigating kinetic isotope effects and quantitative methods of non-mass spectrometry-based stable isotope dilution assay (non-MS SIDA). The separations of 47 isotopologue pairs of common compounds and drugs were achieved by gas-liquid chromatography, employing twelve different stationary phases. Polydimethylsiloxane phase, phenyl substituted polydimethylsiloxane phases, wax phases, ionic liquid phases, and chiral stationary phases were selected to encompass a wide polarity range and diverse chemical interactions. The best-performing stationary phases are presented for separation of protic-polar, aprotic-dipolar, nonpolar analytes. Overall, the IL111i, SPB-20, and PAG stationary phases were remarkable in their ability to separate the isotopologues. The isotope effect was also evaluated. It was observed that nonpolar stationary phases often exhibit an inverse isotope effect in which heavier isotopic compounds elute earlier than their lighter counterparts. Conversely, polar stationary phases often show a normal isotope effect, while those of intermediate polarities can show both effects depending on the isotopologues. The location of deuterium atoms, however, affects isotopologue retention times. Deuterium substituted aliphatic groups appear to have a greater inverse isotope effect on retention than aromatic substituents.

A hydrolytically stable amide polar stationary phase for hydrophilic interaction chromatography

A novel amide functionalized polar stationary phase has been described by grafting acrylamide polymer coating onto hydrolysed poly (glycidyl methacrylate-divinylbenzene) (GMA-DVB) microsphere. The grafting of acrylamide coating is performed via free radical polymerization of acrylamide with pendant double bonds of hydrolysed GMA-DVB microsphere. The obtained stationary phase (G-pAM) possesses favorable hydrophilicity, as proved by strong retention and good separation ability towards several types of model polar analytes (e.g. 71913 plates/m plate count of sucrose), and excellent hydrolytically stability, as indicated by extremely low bleed level (much superior to commercial ones, ~23.7-fold–~77.4-fold lower). Negligible baseline drift under gradient elution (water fraction even up to 50%) was observed. It also exhibits good selectivity in the separation of isomers and homologue sugars.

Influence of the nature of organic solvents on the process of separation of antioxidative additive in a transformer oil by a gas-chromatographic method

THE PURPUSE. The paper considers the influence of the nature of organic solvents on the process of separation of an antioxidant additive added to transformer oil at a concentration of up to 0.40% by weight, and organic solvents used as selective extractants. Based on the analysis of literature data, it is shown that mineral transformer oil is a complex hydrocarbon composition that undergoes oxidative degradation during operation, leading to aging of transformer oil and deterioration of technical conditions of operation of transformer electrical equipment. As a result of this process, peroxide compounds appear in transformer oil, which affect its color, oxidation stability, aging resistance, compatibility with structural parts of equipment, etc. Gas -liquid chromatography was used to determine the "Ionol" antioxidant additive and organic extractants in transformer oil. Experiments were performed on a chromatograph of Chromosomes GC -1000 with a flame ionization detector and a quartz capillary column 30 m long, 0.32 mm in diamet er, filled with a fixed liquid phase Valko Bond VB-WAX P/n with a film thickness of 0.5 microns. The sample was dosed into the gas-liquid chromatograph injector using an automatic liquid dispenser DAZH-23, designed for entering up to twenty-three samples of sorbates and controlled by a computer with the appropriate software.METHODS. Aliphatic alcohols from C1 to C5 were studied as extractants of the antioxidant additive, which are well separated from the ionol both under isothermal conditions and in the mode of linear programming of the column temperature from 40 to 220 °C. Under these conditions the chromatogram of the separation of antioxidant additives, and aliphatic alcohols, which are used to calculate their relative retained volumes, the asymmetry of chromatographic peaks and the column efficiency, which depends on the physico -chemical nature of the solutes to be analyzed and the conditions of the chromatographic experiment.RESULTS. The dependence of the relative volume of retention of aliphatic alcohols on their permittivity, which has a nonlinear form, is established. At the same time, with a decrease in the chain length of alkyl substituents in the aliphatic alcohol molecule, there is a tendency to increase their permittivity. The dependence of the relative retained volume of aliphatic alcohols on the selectivity coefficient of separation with Ionol is linear. In this case, the most optimal separation selectivity, approaching one, is characteristic of the Ionol – Butanol-1 pair. It is shown that the dependence of the logarithm of the retention time of aliphatic alcohols on their boiling points is linear both at a low temperature of the chromatographic column (40 °C) and at a higher temperature (more than 100 °C). CONCLUSION. At the same time, the angle of inclination of the corresponding lines changes in the boiling point of organic solvents, which is associated with a change in the sorption mechanism in a capillary chromatographic column filled with a polar stationary phase.

High efficiency functionalized hydrophilic cyclofructans as stationary phases in sub/supercritical fluid chromatography

Packed column SFC has become very popular for preparative and analytical separations due to the low cost of CO2, its accessible critical temperature, and pressure, with the additional benefit of a low environmental burden. Currently, there is a shortage of new polar stationary phase chemistries for SFC. In this work, two new functionalized cyclofructan columns are introduced and evaluated for their performance in achiral SFC separations for the first time. Cyclofructan (CF6), a macrocyclic oligosaccharide, was covalently linked with benzoic acid (BCF6) and propyl sulfonic acid (SCF6) groups by ether bonds. Superficially porous particles (2.7 μm) bonded with modified CF6 showed markedly different selectivity than native CF6. In SFC, peak shapes of amines and basic compounds are often compromised. We show that small quantities (~5.7% v/v) of water added to the methanol modifier in CO2 improves peak symmetries of primary, secondary, and tertiary amines. Efficiencies as high as 200,000 plates/m (reduced plate height ~ 1.8) were observed for benzamide and amitriptyline on the BCF6 column. The relative standard deviations (RSDs) of retention times on BCF6 were about 1.4%, and on SCF6 were less than 1%. Amines on the SCF6 column showed plate counts as high as 170,000 plates/m. Tetramethylammonium acetate is examined as an alternative to water in MeOH. A run time of 36 min with methanol, trifluoroacetic acid, triethylamine mobile phase was reduced to <5 min with complete baseline resolution for a set of amines. The new stationary phases allow greener approaches towards solving separation problems.

Ensemble hologram quantitative structure activity relationship model of the chromatographic retention index of aldehydes and ketones

色谱保留指数(retention index, RI)是色谱分析中的重要参数,不同化合物在不同极性固定相上具有不同的保留行为。醛酮化合物种类众多,实验测定其RI值的时间和经济成本高。该论文采用集成建模(ensemble modeling)结合全息定量构效关系(HQSAR)方法研究了醛酮化合物在2种固定相(DB-210和HP-Innowax)上色谱保留指数的定量构效关系(QSAR)模型。用外部测试集验证法和留一交叉验证法评估了所建立模型的预测能力。首先建立了34种被研究化合物的个体HQSAR模型。在固定相DB-210上,片段特性(FD)为“供体/受体原子(DA)”且片段尺寸(FS)为1~9时可得到最优个体模型,在固定相HP-Innowax上,FD为“DA”且FS为4~7时可得到最优个体模型,这两个模型的交叉验证相关系数( )分别为0.935和0.909,外部验证相关系数( )分别为0.925和0.927,一致性相关系数(CCC)分别为0.953和0.960,预测平方相关系数F2( )分别为0.922和0.918,预测平方相关系数F3( )分别为0.931和0.927。研究结果表明醛酮化合物的分子结构与RI值之间存在定量关系,用HQSAR方法可以建立二者之间的QSAR模型。其次,以4个预测准确度最高的个体HQSAR模型作为子模型通过算术平均建立了集成HQSAR模型。建立的集成HQSAR模型预测被研究化合物在DB-210和HP-Innowax固定相上RI值的 分别为0.927和0.919, 分别为0.929和0.963, CCC分别为0.956和0.979, 分别为0.927和0.958, 分别为0.935和0.963。与个体HQSAR模型相比,建立的集成HQSAR模型预测准确度更高。这说明集成建模是提高HQSAR模型预测能力的有效方法,HQSAR与集成建模方法相结合可以用于研究和预测醛酮化合物的RI值。

The influence of temperatures, polarity, modifier and pressure to retention index in supercritical fluid chromatography: A review

Changes in analysis parameters affect the retention index calculation on all chromatography systems. In Supercritical Fluid Chromatography, the analysis parameters are more than Gas Chromatography or Liquid Chromatography. In this study, the effect of all those parameters were presented based on the research that has developed to date. The data and the information were collected from the previous published articles. The changes in the analysis parameters which are temperature, polarity, modifier, and pressure on SFC affected the retention index calculation, but the significant levels were different. The pressure change has the least significant effect for both polar and non-polar analytes. The temperature and stationary phase polarity changes have insignificant effects for non-polar analyte, but significant for polar one. Meanwhile, the modifier change have a very significant effect, both for polar and non-polar analytes.

Improvement of the gas chromatographic method for diagnosing developing defects in oil-filled electrical equipment based on the analysis of furan compounds

During the operation of oil-filled electrical equipment under the influence of temperature, humidity and other negative factors, the destruction of paper insulation occurs. As a result of this destruction, furan compounds are formed, which get into the transformer oil. To identify the process of destruction of paper insulation, control of furan compounds in transformer oil is carried out by instrumental methods. Of these methods, the most widely used is gas chromatography using packed chromatographic columns, on the basis of which guidelines have been developed. To improve gas chromatographic methods for monitoring furan compounds, we used a highly efficient quartz capillary column filled with a polar stationary phase based on polyethylene glycol. The sample was injected into the injector of the chromatograph Chromos-GC1000 using an automated dosing system with a vial for 23 samples. Used transformer oil of the GK-1 brand of Almetyevsk electrical networks was taken as the object of research; The optimal retention characteristics of standard sorbates were preliminary determined, which were used as organic extractants of transformer oil and furan compounds. The effect of temperature on the process of chromatographic analysis of furfuryl alcohol and organic extractants was determined, on the basis of which it was established that the selectivity of separation is determined by the nature of intermolecular interactions in the sorbate-sorbent system, in particular, the formation of a hydrogen bond. It has been shown that the selectivity coefficient for the separation of furfuryl alcohol depends on the physicochemical nature of organic extractants, their boiling points and dipole moments and has the highest values for the analyzed pair of components: furfuryl alcohol - ethanol.

Polar polymer-immobilized stationary phase for aqueous reversed-phase liquid chromatography

In this work, a polar stationary phase was prepared by thermal immobilization of poly(glycidoxypropylmethyl-co-dimethylsiloxane) onto silica particles to separate polar compounds using water-rich mobile phases. The retention properties of the stationary phase were characterized by the separation of Tanaka and NIST SRM® 870 test mixtures. The elution order of the compounds indicated the reversed-phase mode, but the stationary phase was less hydrophobic and with higher silanophilic activity than typical stationary phases. Polar compounds presented reasonable retention in the stationary phase and symmetrical peaks in the chromatograms, due to hydrophilic interactions with glycidoxy groups in the polymer side chain. The stationary phase was applied for the separation of small polar and ionizable compounds. The retention factors increased with the aqueous mobile phase component. So, all polar compounds were separated efficiently and eluted symmetrically under highly aqueous mobile phases, >90%. Per aqueous liquid chromatography was the principal separation mode of the new stationary phase, presenting as a green alternative to the hydrophilic interaction liquid chromatography mode for the separation of polar compounds.

An eco-friendly micellar HPLC method for the simultaneous determination of triamterene and xipamide in active pharmaceutical ingredients and marketed tablet dosage form

AbstractIn the last few years, the use of surfactants as mobile phase additives in reversed phase liquid chromatography (RPLC) has been steadily developing and improving. Surfactants modify the polarity of the stationary phase which in turn decreases the amount of organic solvent required for elution of the analytes rendering the methodologies linked to them greener and more eco-friendly. Brij-35 is a fatty alcohol ethoxylates non ionic surfactant, which is less widely used as mobile phase additive. Brij-35 can decrease stationary phase polarity while remaining neutral. In this research, Brij-35 was studied in the separation and determination of marketed antihypertensive combination therapy composed of triamterene (TRM) and xipamide (XIP). TRM and XIP are diuretics used for treatment of essential hypertension and associated edema conditions. Chromatographic separation was achieved on RP-C18 column (Kinetix®, 5 µm, 15 cm × 4.6 mm) at flow rate 1 mL min−1 and UV-detection at 254 nm. Isocratic elution was performed using mobile phase composed of 0.1 M Brij-35: methanol (MeOH) (60:40, v/v). The analytes were well separated and quantified within linearity ranges of 5–50 µg mL−1 for both drugs in short retention time (2.6 and 5.3 min. for TRM and XIP, respectively). Since claiming greenness is not enough, Green Analytical Procedure Index (GAPI) was used to demonstrate the superiority of the proposed method over the previously reported methods. GAPI is a new metric for evaluation of the ecological impact of analytical procedures. The proposed method was validated according to ICH guidelines and applied successfully for simultaneous determination of the drugs in their co-formulated tablets.

Carbon Nanotube (CNT) Stationary Phase for Micro Gas Chromatograph Columns

Introduction Microfabricated gas chromatography systems based upon MEMS fabrication technology are under development for portable chemical vapor analysis and chemical detection. In particular, Sandia National Laboratories has pioneered development of these miniature systems (1). Current methods for coating microfabricated gas chromatography columns are based upon deposition from a saturated mixture of siloxanes in a solvent, which are adapted from techniques developed for coating of open-tubular capillary columns (2). This static method is more successful with silica open tube columns which have a uniform cross-section area, however in a microfabricated column, a rectangular cross-section is produced in the channel. The square corners tend to have a thicker layer of material deposited using this process and hence these thicker layers provide a different retention time for the analytes which results in peak broadening and reduction in resolution and peak capacity of the column. Alternative stationary phases have been investigated (3), and using chemical vapor deposition (CVD) they can be grown with uniform thickness, for example carbon nanotubes (CNTs) (4) The CNTs have high surface area and are stable at high temperatures. Method A silicon substrate is used for the fabrication of a microfabricated spiral column, 6m in length using standard photolithography and deep reactive ion etching fabrication processes (5). An ultra-thin layer of iron catalyst is deposited by sputtering into the etched silicon channel. Using a Black Magic plasma enhanced CVD growth a layer of CNTs are formed thickness 0.5 to 1 micrometer. Figure 1 shows an SEM micrograph of the deposited CNTs layer which coats the sides of channel and base with uniform thickness. Next a layer of gold is deposited for eutectic bonding of the silicon lid in order to enclose the channel making the column. Finally high temperature annealing is carried out at 450 oC to increase bond strength. Results The column is mounted inside a commercial Agilent 6890 GC system oven with a short length of guard column, approximately 0.5m length, connect between the split injector and the flame ionization detector. A liquid injection of three compounds, hexane, octane and decane, volume of 0.02uL, was carried out with a 100:1 split and injector temperature of 275°C. The helium carrier gas flow rate was 0.1 ml/min. A typical chromatogram is shown in Figure 2. The McReynolds probes for polarity were also injected, and the Kovats indices were evaluated for comparison with OV-1 (Ohio Valley, OH) polymer stationary phase. Conclusions The use of CNT’s for a stationary phase may offer some advantages with micro-GC column fabrication because the quality of the layer can be inspected prior to bonding. We can observe the low polarity of the CNT stationary phase compared to the poly-siloxane However, it may be possible to chemically functionalize the surface for the CNTs for more polar compound separation and analysis.

Enhancing supercritical fluid chromatographic efficiency: Predicting effects of small aqueous additives

Supercritical fluid chromatography is becoming more prevalent, particularly in industry. This is due to the inexpensive, and more importantly, environmentally benign carbon dioxide that is used as the major component of the mobile phase. Water is minimally miscible with carbon dioxide at temperatures and pressures commonly used in SFC. However, the introduction of a polar alcohol modifier component increases the solubility of water in carbon dioxide. Previously, the addition of small amounts of water in the mobile phase was shown to provide significant gains in efficiency in chiral supercritical fluid chromatography, especially with polar stationary phases. In this work, we report the effect of the addition of small amounts of water on efficiency and retention factor with four different SFC stationary phases used for achiral analysis namely FructoShell-N (native cyclofructan-6), SilicaShell (bare silica), PoroShell 120 EC C18 (octadecyl silica) and Xselect C18 SB. This is the first reported use of FructoShell-N, a cyclofructan derivatized phase for SFC applications. We devised a predictive test to determine which analytes show an increase in efficiency using their known chemical constants (logKow, pKa, PSA and Hsum). We also use discriminant analysis to elucidate the most important analyte parameters that contribute to “water enhanced” efficiency gains.

Exploiting the versatility of vacuum-assisted headspace solid-phase microextraction in combination with the selectivity of ionic liquid-based GC stationary phases to discriminate Boswellia spp. resins through their volatile and semivolatile fractions.

The frankincense resins, secreted from Boswellia species, are an uncommon example of a natural raw material where every class of terpenoids is present in similar proportions. Diterpenoids (serratol, incensole, and incensole acetate) are used to discriminate samples from different species and origins. Headspace solid-phase microextraction has been used for frankincense analysis, although it requires long sampling time for medium- to low-volatility markers; headspace solid-phase microextraction under vacuum can overcome this limit. Gas chromatography is used for analysis but the separation of incensole and serratol needs polar stationary phases. In this study, we develop a method to discriminate frankincenses based on vacuum-assisted headspace solid-phase microextraction combined with fast gas chromatography-mass spectrometry with ionic liquid-based stationary phases. The optimized conditions for solid samples were: air evacuation below 0°C, 15min of incubation time, and 15min of extraction time. Losses of volatiles due to vial air-evacuation in the presence of the sample were minimized by sample amount above 100mg and low sample temperature. Fast gas chromatography provides the baseline separation of all markers in 20min. By applying vacuum sampling and fast gas chromatography, the total analysis was reduced to 50min compared to 120min (60min sampling plus 60min analysis) as previously reported. The method was successfully applied to commercial frankincense samples.

Advances in Asphaltene Petroleomics. Part 4. Compositional Trends of Solubility Subfractions Reveal that Polyfunctional Oxygen-Containing Compounds Drive Asphaltene Chemistry

Asphaltenes have traditionally been conceived as highly aromatic, alkyl-deficient compounds enriched in pericondensed aromatic “island” motifs. This structural definition evolved into the general notion that aromatic core-dominated interactions (π-stacking) drive asphaltene aggregation, and heteroatom-based intermolecular forces have no significant effect on the overall solubility and aggregation behavior. However, the exclusion of heteroatoms in asphaltene chemistry is inconsistent with the Boduszynski continuum and known asphaltene properties, such as increased heteroatom content relative to maltenes, interfacial activity, and strong adsorption to polar stationary phases. Thus, to determine whether or not heteroatoms are involved in solubility, we have separated asphaltene fractions enriched in single-core (island) or multicore motifs (archipelago) according to their partitioning in n-heptane by two fractionation methods. In the first separation procedure, the acetone fraction from Wyoming deposit n-heptane asphaltenes (island-enriched) was adsorbed on polytetrafluoroethylene powder and Soxhlet extracted with n-heptane. Subfractions were collected after one day, one week, one month, and three months of extraction, and the residue, n-heptane insoluble material, was recovered with a mixture of toluene and dichloromethane. In the second method, the acetone fraction from Athabasca bitumen n-heptane asphaltenes (archipelago-enriched) was fractionated by differential precipitation in mixtures of n-heptane and toluene. The molecular composition of the asphaltene subfractions was accessed by positive-ion atmospheric pressure photoionization coupled to 9.4 T Fourier transform ion cyclotron resonance mass spectrometry and structures were determined by infrared multiphoton dissociation. The compositional trends for heteroatom content, double bond equivalents, and alkyl substitution suggest that the Boduszynski continuum can be extended to asphaltenes. In particular, the compositional range of polyoxygenated asphaltene compounds shifts toward lower aromaticity, whereas oxygen-depleted species are more aromatic. Moreover, the results demonstrate that polyoxygenated species (e.g., O₃ and S₂O₃ classes) are pivotal in asphaltene solubility, as they concentrate in the most polarizable and insoluble asphaltene subfractions. Therefore, the results support the existence of atypical asphaltene species with remarkably low aromaticity that reside in the most insoluble asphaltene subfractions because of their high heteroatom content. Such asphaltene compounds preferentially ionize as protonated molecules rather than radical cations and overlap the compositional range of interfacially active species, consistent with their tendency to participate in hydrogen bonding. Collectively, the results highlight the need for an asphaltene molecular model based on the existence of polyfunctional species capable of interacting with neighboring asphaltene molecules through several intermolecular forces, including London dispersion forces between aliphatic moieties, π-stacking of aromatic cores, hydrogen bonding between nitrogen and oxygen-containing functionalities, and acid/base interactions between carboxylic acids and pyridine rings.

Характеристика неподвижных фаз для газовой хроматографии

The methods of preferred stationary phases choosing the used in gas-liquid chromatography are analyzed. It is shown that in the literature, such criteria as selectivity, sorption capacity, thermal stability, reproducibility of properties, operating temperature range, etc. are used as criteria for choosing suitable stationary phases. One of the most used methods for characterizing stationary phases is their classification using chromatographic polarity based predominantly on the values of polarity factors proposed by Rorschneider and Mc Reynolds. The basis of these systems is the characterization of various types of intermolecular interactions into which stationary phases can enter, using a set of standard substances. The system of Rorschneider-McReynolds polarity factors is also the basis of the spectral approach to identifying the components of complex mixtures, the essence of which is to use the combination of physicochemical characteristics of the sorbate and sorbent, which allows to establish the structure of sorbate molecules based on their different ability to be sorbed by stationary phases of different chemical nature. The spectral approach is applied to the characterization of weakly polar stationary phases of various chemical nature. It was shown that despite the close chromatographic polarity of the stationary phases, the retention of substances belonging to different classes of compounds can significantly differ and be determined by the values of descriptors characterizing the types of intermolecular interactions and the tendency of the stationary phases to a certain type. Spectra of 5 stationary phases obtained using the Rorschneider, Mac-Reynolds, and Lafffort solubility factors are presented. It was established that the possibility of preferential retention of sorbates of various chemical nature is determined by the ratio between the values of these descriptors. The possibility of choosing the corresponding stationary phases for the selective separation of sorbates of various chemical nature is shown.

Evaluating MISER chromatography as a tool for characterizing HILIC column equilibration

Hydrophilic Interaction Liquid Chromatography (HILIC) is a technique for retaining polar analytes that uses polar stationary phases and acetonitrile-rich mobile phases. While this technique has several advantages over reversed-phase liquid chromatography (RPLC), one main drawback is the reported need for longer column equilibration. The reason for this is not fully understood and is a topic of current investigation. In order to better understand and reduce the equilibration needs, accurate characterization of column equilibration under varying conditions is required. The current method of characterizing HILIC column equilibration produces limited data points per test, or low time resolution, and is highly dependent on the column and probe compounds being used. There is a need for an improved method for characterizing HILIC column equilibration, especially if trends across stationary phases are to be observed. In this work, MISER, or Multiple Injections in a Single Experimental Run, is evaluated as a possible tool for characterizing HILIC column equilibration. MISER improves time resolution by allowing for replicate injections without interruption of data collection, enabling a more thorough evaluation of column equilibration compared to traditional techniques. Experimental results gathered using MISER show that equilibration of a BEH Amide column is notably shorter when equilibrating from acetonitrile to mobile phases containing higher percentages of water. Column equilibration to a 10% aqueous mobile phase was found to be approximately 5-fold faster than equilibration to a 3% aqueous mobile phase.