Octadecyl Ligands Research Articles

Design and construction of fluorine-free, cost-effective and robust superhydrophobic coatings using nanosilica with highly covalently bonded octadecyl ligands

Low surface energy and rough structure are two key factors in achieving superhydrophobicity. Currently, one of the common routes to acquire low surface energy is via the hydrolytic modification of organosilanes. However, due to steric hindrance, self-condensation of hydrolyzed silanes predominates, whereby the resulting products are mainly physically adsorbed or attached to the substrate by few bonds, resulting in the formed superhydrophobic surfaces susceptible to damage by external forces, which significantly inhibits their practical application and long-term service. Herein, we prepared a novel functionalized nanosilica with highly chemically grafted octadecyl ligands in a non-aqueous medium. The covalent bond structure of the product (ODS@SiO2) is approved, and an average grafting density of 10 chains nm−2 was calculated. The ODS@SiO2 has a crystal structure and displays superior thermal and chemical resistance. ODS@SiO2 can be homogeneously dispersed in n-hexane and then applied to various substrates pre-coated with an adhesive by directly spraying or dip-coating to create superhydrophobic coatings. Studies demonstrate that the aggregation of the ODS@SiO2 with high grafting octadecyl ligands on a substrate not only provides a stable low-surface energy layer but also creates multi-level hierarchical structures and microspheres, thus strengthening the robustness of the coating. The coatings exhibit excellent water repellency and self-cleaning ability while maintaining superhydrophobicity after multiple cycles of mechanical abrasion and exposure to harsh environmental conditions. We convince that the fluorine-free, cost-effective and robust superhydrophobic coating has potential applications in various fields.

Poly(carboxyethyl acrylate‐co‐ethylene glycol dimethacrylate) precursor monolith with bonded octadecyl ligands for use in reversed‐phase capillary electrochromatography

A carboxy precursor monolithic column, namely poly(carboxy ethyl acrylate-co-ethylene glycol dimethacrylate) was first produced in a 100μm i.d. fused-silica capillary and subsequently surface bonded with n-octadecyl (C18 ) ligands by a post-polymerization functionalization process with octadecylamine in the presence of N,N´-dicyclohexylcarbodiimide. The bonding of octadecyl ligands was achieved via an amide linkage between the carboxy functions of the precursor monolith and the amino group of the octadecylamine compound. The resulting C18 monolith exhibited a very low electroosmotic flow (EOF), a fact that required the incorporation of small amounts of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) in the polymerization solution to produce a precursor monolith with fixed negative charges of sulfonate groups. This may indicate that the conjugation of the carboxy functions with octadecylamine occurred to a large extent so that the amount of residual carboxy functions was sparsely dispersed and not enough to produce a desirable EOF. The EOF velocity of the C18 column having fixed negative charges provided by the incorporated AMPS increased with increasing ACN content of the mobile phase signaling an increased binding of mobile phase ions to the polar amide linkages near the monolithic surface, and a decreased viscosity of the mobile phase, both of which would result in increased EOF velocity. The C18 monolithic column constituted a novel nonpolar sorbent for reversed-phase capillary electrochromatography for nonpolar solutes, e.g., alkylbenzenes, alkylphenyl ketones, and polyaromatic hydrocarbons, and slightly polar compounds including phenol and chlorophenols. The C18 monolithic column exhibited relatively high selectivity toward chlorophenols differing by one chloro substituent.

Benefits of Innovative and Fully Water-Compatible Stationary Phases of Thin-Film Microextraction (TFME) Blades.

Octadecyl (C18) groups are arguably the most popular ligands used for preparation of solid phase microextraction (SPME) devices. However, conventional C18-bonded silica particles are not fully compatible with the nearly 100% aqueous composition of typical biological samples (e.g., plasma, saliva, or urine). This study presents the first evaluation of thin-film SPME devices coated with special water-compatible C18-bonded particles. Device performance was assessed by extracting a mixture of 30 model compounds that exhibited various chemical structures and properties, such as hydrophobicity. Additionally, nine unique compositions of desorption solvents were tested. Thin-film SPME devices coated with C18-bonded silica particles with polar end-capping groups (10 µm) were compared with conventional trimethylsilane end-capped C18-bonded silica particles of various sizes (5, 10, and 45 µm) and characteristics. Polar end-capped particles provided the best extraction efficacy and were characterized by the strongest correlations between the efficacy of the extraction process and the hydrophobicity of the analytes. The results suggest that the original features of octadecyl ligands are best preserved in aqueous conditions by polar end-capped particles, unlike with conventional trimethylsilane end-capped particles that are currently used to prepare SPME devices. The benefits associated with this improved type of coating encourage further implementation of microextractraction as greener alternative to the traditional sample preparation methods.

Poly(2-carboxyethyl acrylate-co-ethylene glycol dimethacrylate) precursor monolith. Part I. Carbodiimide assisted post-polymerization modification with octadecyl ligands for use in reversed phase capillary liquid chromatography

In this proof of concept study, a new precursor monolithic column was prepared by the in situ co-polymerization of 2-carboxyethyl acrylate (CEA) and ethylene glycol dimethacrylate (EDMA) in a 300 μm i.d. fused silica capillary yielding a poly(CEA-co-EDMA) monolithic column. This carboxy monolith precursor with its surface carboxyl groups was subsequently subjected to post-polymerization modification with octadecylamine (ODA) via a carbodiimide conjugation reaction. The carbodiimide with its zero-length carboxyl-to-amine coupling ability works by activating the surface carboxyl groups of the monolith for direct reaction with the primary amines of ODA via amide bond formation. This reaction, which is applied for the first time in monolithic column fabrication, yielded the octadecyl-poly(CEA-co-EDMA) monolithic capillary column for use in reversed phase capillary LC. This octadecyl column was evaluated for its RPC retention property with alkylbenzenes (ABs) and alkyl phenyl ketones (APKs). The methylene group selectivity (αCH2) in the particular homologs was about the same for both ABs and APKs (αCH2 = 1.6) using the same mobile phase composition. This may indicate that the retention mechanism is the same for both homologous series. The retention behaviors of polyaromatic hydrocarbons and chlorophenol compounds were also examined on the octadecyl capillary column.

Poly (N-acryloxysuccinimide-co-ethylene glycol dimethacrylate) precursor monolith and its post polymerization modification with alkyl ligands, trypsin and lectins for reversed-phase chromatography, miniaturized enzyme reactors and lectin affinity chromatography, respectively.

This investigation was aimed at introducing a monolithic precursor that can be conveniently grafted with the desired chromatographic ligand via the process of post polymerization modification (PPM). The precursor was obtained by the in-situ polymerization of N-acryloxysuccinimide (NAS) and ethylene glycol dimethacrylate (EDMA) in a narrow bore stainless steel column of 1mm i.d. yielding a poly(NAS-co-EDMA) monolithic column designated as the poly(NAS-co-EDMA) monolith (NASM) column. In a first PPM, the NASM column was bonded with octadecyl (OD) ligands yielding a nonpolar NASM-OD column that proved useful for reversed phase chromatography (RPC) of proteins in gradient elution at increasing %ACN in the mobile phase. NASM-OD resulted from the reaction between the N-hydroxysuccinimide of NASM with octadecyl amine. In a second PPM, NASM was surface immobilized with trypsin generating a proteolytic narrow bore enzyme reactor called NASM-trypsin immobilized enzyme reactor (IMER) that permitted the online digestion of proteins in a 20-min single pass through the IMER incorporated in a setup equipped with a short RPC column to achieve simultaneously a peptide tryptic map. This constituted a rapid turnover whereby ∼95% of the protein was hydrolyzed by the immobilized trypsin. In a third PPM, the NASM column was surface immobilized with three different lectins (LCA, Con A and RCA) having complementary affinities toward serum glycoproteins thus permitting the capture of a wide range of glycoproteins/glycoforms. The three NASM-lectin columns when operated in a tandem format led to assessing the level of the various glycoforms in human serum via LC-MS/MS analysis of the captured protein fractions by each NASM-lectin column.

Multilayer adsorption in liquid chromatography – The surface heterogeneity below an adsorbed multilayer

A numerical method was introduced for the estimation of the surface heterogeneity below an adsorbed multilayer of the analyte. The calculation procedure is based on the raw adsorption isotherm data points obtained by frontal analysis experiments. To permit the mapping of the nature of the analyte–surface interaction, a numerical procedure was used to pre-estimate the adsorbate–adsorbate interactions occurring during the adsorption process. The surface heterogeneity estimation was carried out using the affinity-energy distribution calculations with assuming local BET isotherm. In the local BET isotherm the pre-estimated adsorbate–adsorbate interaction constant was used, and the surface heterogeneity was described. After the test of the numerical method with benchmark isotherms, the algorithm was tested on several experimental isotherms. The isotherms were measured using phenol as test molecule on reversed phase adsorbents, with different surface coverage of the octadecyl ligands. The surface of the non-end-capped stationary phases showed detectable heterogeneity, while the surface end-capped phases were found to be homogeneous.

Monolithic stationary phases with incorporated fumed silica nanoparticles. Part II. Polymethacrylate-based monolithic column with “covalently” incorporated modified octadecyl fumed silica nanoparticles for reversed-phase chromatography

This study is concerned with the incorporation of surface modified fumed silica nanoparticles (FSNPs) into polymethacrylate based monolithic columns for use in reversed phase chromatography (RPC) of small solutes and proteins. First, FSNPs were modified with 3-(trimethoxysilyl)propylmethacrylate (TMSPM) to yield the “hybrid” methacryloyl fumed silica nanoparticle (MFSNP) monomer. The resulting MFSNP was then mixed with glyceryl monomethacrylate (GMM) and ethylene dimethacrylate (EDMA) in a binary porogenic solvent composed of cyclohexanol and dodecanol, and the in situ copolymerization of MFSNP, GMM and EDMA was performed in a stainless steel column of 4.6 mm i.d. The silanol groups of the hybrid monolith thus obtained were grafted with octadecyl ligands by perfusing the hybrid monolithic column with a solution of 4% w/v of dimethyloctadecylchlorosilane (DODCS) in toluene while the column was maintained at 110°C for 6h (in a heated HPLC oven). One of the originalities of this study was to demonstrate MFSNP as a novel derivatized “hybrid monomer” in making RPC monolithic columns with surface bound octadecyl ligands. In this respect, the RPC behavior of the monolithic column with “covalently” incorporated FNSPs having surface grafted octadecyl ligands was evaluated with alkylbenzenes, aniline derivatives and phenolic compounds. The results showed that the hybrid poly(GMA-EDMA-MFSNP) having surface bound octadecyl ligands exhibited hydrophobic interactions under reversed phase elution conditions. Furthermore, six standard proteins were baseline separated on the column using a 10min linear gradient elution at increasing ACN concentration in the mobile phase at a flow rate of 1.0mL/min using a 10 cm×4.6mm i.d. column. The relative standard deviations (RSDs) for the retention times of the tested solutes were lower than 2.1% and 2.4% under isocratic elution and gradient elution conditions, respectively.

Ligand-Mediated Interactions between Nanoscale Surfaces Depend Sensitively and Nonlinearly on Temperature, Facet Dimensions, and Ligand Coverage.

Nanoparticles are often covered in ligand monolayers, which can undergo a temperature-dependent order-disorder transition that switches the particle-particle interaction from repulsive to attractive in solution. In this work, we examine how changes in the ligand surface coverage and facet dimensions affect the ordering of ligands, the arrangement of nearby solvent molecules, and the interaction between ligand monolayers on different particles. In particular, we consider the case of strongly bound octadecyl ligands on the (100) facet of CdS in the presence of an explicit n-hexane solvent. Depending on the facet dimensions and surface coverage, we observe three distinct ordered states that differ in how the ligands are packed together, and which affect the thickness of the ligand shell and the structure of the ligand-solvent interface. The temperature dependence of the order-disorder transition also broadens and shifts to lower temperature in a nonlinear manner as the nanoscale is approached from above. We find that ligands on nanoscale facets can behave very similarly to those on macroscopic surfaces in solution, and that some facet dimensions affect the ligand alignment more strongly than others. As the ligands order, the interaction between opposing monolayers becomes attractive, even well below full surface coverage. The strength of attraction per unit surface area is strongly affected by ligand coverage, but only weakly by facet width. Conversely, we find that bringing two monolayers together just above the order-disorder transition temperature can induce ordering and attraction.

Preparation of octadecyl methacrylate-based polymer stationary phase by in-situ polymerization for open tubular capillary electrochromatography

The preparation of porous polymethacrylate-based open tubular capilary columns by in-situ copolymerization of octadecyl methacrylate (OMA), and ethylene dimethacrylate (EDMA) in N,N-dimethylformamide (DMF) solvent are proposed. The parameters of the preparation procedure of the stationary phase are discussed in detail. The surface of the cross-section of an open tubular (OT) column by scanning electron microscope (SEM) showed wrinkle configuration, which is expedient to enhance proportion of stationary phase and column capacity. Efficient separation of six alkyl benzene homologous series (namely, toluene, ethylbenzene, propylbenzene, butylbenzene, amylbenzene and hexylbenzene) were performed by CEC using the prepared column, and their elution order was in agreement with their hydrophobicity. So, the OT columns bonded with octadecyl ligands yielded reversed-phase retention behavior toward nonpolar solutes. In addition, the separation of four antiepileptics was also investigated with satisfactory effectiveness. The column efficiency range was 35 300-49 800 plates/m. The results showed that the C18-OT column of organic matrix for reversed-phase chromatography was successfully prepared via in-situ polymerization in this work. Hereby, this new column thus offers a promising new alternative in OT-CEC and will be useful in separation science.

Thermodynamics Study of Solvent Adsorption on Octadecyl-Modified Silica.

Elution and solvation processes in liquid chromatography may be controlled by temperature changes. In the case of solvent adsorption, the temperature influences the amount of adsorbed solvent as well as the enthalpy and entropy of the solvation process. In this work, the thermodynamic parameters of organic solvents used as organic modifiers in the reversed-phase high-performance liquid chromatography elution process were determined. The changes of enthalpy and entropy in a series of chemically bonded stationary phases were measured to determine the effects of the temperature and surface coverage density of octadecyl ligands on the thermodynamic parameters of the solvation. For both the enthalpy and entropy a parabolic trend was observed with the minimum for medium surface coverage. The correlation of solvent adsorption values with the enthalpy of solvation was also investigated. The highest influence of the temperature on solvation process was observed for stationary phases with high surface coverage.

Study of hydration process on silica hydride surfaces by microcalorimetry and water adsorption

A series of hydrosilated stationary phases were compared with respect to their hydrophilic–hydrophobic properties. The stationary phases were also compared to the bare silica gel used for this synthesis. The investigations were done using microcalorimetric measurements of methanol and acetonitrile heats of immersion. Because these stationary phases are used in both the reversed-phase and aqueous normal phase modes of liquid chromatography, the excess isotherm of water from acetonitrile solution was measured.From the materials tested the highest polarity was exhibited by the silica hydride and the bare silica. The Diamond Hydride is less polar. The highest hydrophobicity is exhibited by the hydrosilated stationary phase which contains bonded octadecyl ligands.

Two-dimensional high-performance thin-layer chromatography of tryptic bovine albumin digest using normal- and reverse-phase systems with silanized silica stationary phase

Among many advantages of planar techniques, two-dimensional (2D) separation seems to be the most important for analysis of complex samples. Here we present quick, simple and efficient two-dimensional high-performance thin-layer chromatography (2D HPTLC) of bovine albumin digest using commercial HPTLC RP-18W plates (silica based stationary phase with chemically bonded octadecyl ligands of coverage density 0.5μmol/m2 from Merck, Darmstadt). We show, that at low or high concentration of water in the mobile phase comprised methanol and some additives the chromatographic systems with the plates mentioned demonstrate normal- or reversed-phase liquid chromatography properties, respectively, for separation of peptides obtained. These two systems show quite different separation selectivity and their combination into 2D HPTLC process provides excellent separation of peptides of the bovine albumin digest.

Pressurized CEC with amperometric detection using mixed‐mode monolithic column for rapid analysis of chlorophenols and phenol

A simple analysis of chlorophenols (2-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol) and phenol was accomplished by coupling a pressurized CEC with amperometric detection (AD). Efficient and reproducible separation of these compounds was achieved within 9 min on a capillary monolithic stationary phase bonded with octadecyl ligands and sulfonate groups, where the selectivity and the retention of analytes can be functionally controlled by optimizing experimental variables, including organic modifier content, mobile phase pH, ionic strength, working electrode potential, separation voltage, and supplementary pressure. A mixed-mode retention mechanism consisting of reverse-phase chromatographic partition, electrostatic repulsion, and electrophoresis is considered to play roles in the separation. The use of ACN-based media seems effectual in preventing the unfavorable irreversible adsorption on both wall and electrode, and offer higher sensitivity and less electrode fouling in AD of phenols. The LODs were in the range from 0.02 to 0.2 μg/mL with a wide linear dynamic range of 5000-fold, while the peak area precision ranged from 3.2 to 7.5%. The feasibility of using this method in real analysis was evaluated by recovery estimates and comparative experiment on spiked tap water samples. Good recoveries of 80-110% were achieved. Additionally, a paired t-test was used to correlate the two methods.

Effect of polar interactions on the nonlinear behavior of phenol and aniline in reversed phase liquid chromatography

The effect of the coverage density and the activity of the unreacted silanol groups of the non-endcapped octadecyl bonded phase on the adsorption properties were investigated. The adsorption of two polar low molecular weight compounds with weak acidic (phenol) and with basic (aniline) character was measured. Adsorption data were acquired by frontal analysis from methanol–water and acetonitrile–water solutions to investigate the influence of the type of the organic modifier on the solute retention mechanism and adsorption under non-linear conditions. The adsorption behavior of phenol changes from Langmuir type (from aqueous mixture of methanol) to BET type (from aqueous mixture of acetonitrile). The adsorption of aniline becomes BET-type, regardless of the mobile phase composition in the tested range of the surface coverage of octadecyl ligands. The nature of the organic modifier significantly affects the retention mechanism and the shape of the overloaded elution bands of the studied compounds.

Sol–gel coatings with covalently attached methyl, octyl, and octadecyl ligands for capillary microextraction. Effects of alkyl chain length and sol–gel precursor concentration on extraction behavior

Fused silica capillaries with surface-bonded sol–gel coatings containing covalently attached octadecyl, octyl, and methyl groups were prepared for capillary microextraction (CME) hyphenated on-line with high-performance liquid chromatography (HPLC). For this, octadecyltrimethoxysilane (C 18TMS), octyltrimethoxysilane (C 8TMS), or methyltrimethoxysilane (MTMS) was used as the respective sol–gel precursor. Hydrolytic polycondensation of these precursors led to the formation of surface-bonded sol–gel sorbents with pendant alkyl groups ready to serve as the extraction medium; no additional surface derivatization reactions were needed to anchor these ligands to the surface. Extraction behaviors of two sets of microextraction capillaries with alkyl-bonded sol–gel coatings were investigated: (a) capillaries prepared with a constant molar concentration of these precursors in the sol solution, and (b) capillaries prepared with varied molar concentrations of C 8TMS in the sol solution. Among the capillaries prepared using sol solutions with the same molar concentration of sol–gel precursor, the detection limits for nonpolar and polar analytes ranged from 0.3 ng/L to 213.9 ng/L. The sol–gel octadecyl-coated capillaries were found to be the most efficient at extracting these analytes, followed by the sol–gel octyl-coated capillaries, followed by the sol–gel methyl-coated capillaries. The results of this study point to the possibility that polar analytes are extracted through synergistic molecular level interactions of the polar and nonpolar parts of the analyte molecules with the alkyl chains and silanol groups within the sol–gel coatings. These coatings also demonstrated run-to-run and capillary-to-capillary reproducibility, with HPLC peak area RSD values ranging from 1.1% to 9.6% and 1.3% to 10.0%, respectively. In the set of sol–gel octyl capillaries with varied molar concentrations, the capillaries prepared with 0.514 M concentration of C 8TMS in the sol solution were most efficient in extracting nonpolar and polar analytes. When higher or lower concentrations of C 8TMS were used in the sol solution, the resulting sol–gel coated capillaries were less efficient in extracting nonpolar and polar analytes.

Preparation of polymethacrylate monolithic stationary phases having bonded octadecyl ligands and sulfonate groups: Electrochromatographic characterization and application to the separation of polar solutes for pressurized capillary electrochromatography

In this report, the preparation of porous polymethacrylate-based monolithic columns by in situ copolymerization of octadecyl methacrylate (OMA), 3-sulfopropyl methacrylate (SPMA) and ethylene dimethacrylate (EDMA) in a binary porogenic solvent consisting of cyclohexanol/1,4-butanediol are proposed. These monoliths possess in their structures bonded octadecyl ligands and sulfonate groups and are evaluated in pressurized capillary electrochromatography (pCEC) system using small neutral and charged solutes. While the sulfonate groups are meant to generate the electroosmotic flow (EOF) necessary for transporting the mobile phase through the monolithic capillary; the octadecyl ligands are introduced to provide the nonpolar sites for chromatographic retention for neutral solutes. However, incorporating the sulfonate groups in the monoliths does not only support the EOF but also exhibit hydrophilic interaction as well as electrostatic interaction/repulsion with the monoliths in addition to electrophoretic migration with polar charged solutes (e.g., nucleotides). The monolithic stationary phases at different EOF velocities are easily prepared by altering the amount of SPMA in the polymerization solution as well as the composition of the porogenic solvent. Optimum EOF velocity, the highest efficiency and adequate chromatographic retention are obtained when 0.6% SPMA is added to the reaction mixture. Under these conditions, rapid separation and high plate counts reaching greater than 170,000 plates/m are readily obtained.

Influence of stationary phase properties on the separation of ionic liquid cations by RP‐HPLC

Different types of columns with specific structural properties were used for the separation of mixtures of ionic liquid cations. Two of them were home-made packings and the other two were commercial stationary phases. One of the home-made packings contained cholesterol ligands bonded chemically to silica (SG-CHOL) whereas the other one was a mixed stationary phase (SG-MIX) with cyanopropyl, aminopropyl, phenyl, octyl, and octadecyl ligands. RP-18e Innovation ChromolithTM Performance and Macrosphere 300 C4 packings were also used. A comparison of the separation possibilities offered by these columns for the substances in question revealed significant differences in performance. Packings containing surface-bonded functional groups that are able to undergo protonation are not suitable for separation of such compounds under the given analysis conditions (pH = 4). The best results were obtained for two alkyl stationary phases: butyl and octadecyl. Cluster analysis has also been performed for comparison of the ionic liquid cation properties.

Capillary electrochromatography with monolithic-silica columns. II. Preparation of amphiphilic silica monoliths having surface-bound cationic octadecyl moieties and their chromatographic characterization and application to the separation of proteins and other neutral and charged species.

Three different synthetic routes have been introduced and evaluated for the preparation of amphiphilic silica-based monoliths possessing surface-bound octadecyl ligands and positively charged groups. The amphiphilic silica monoliths (designated as cationic C18-monoliths) have been designed for use in reversed-phase capillary electrochromatography (RP-CEC) with hydro-organic mobile phases. These amphiphilic stationary phases yielded anodic electroosmotic flow (EOF) over a wide range of mobile phase pH. The magnitude of EOF remained constant up to pH 4.0 and then decreased at pH > 4.0 due to the ionization of silanol groups and the subsequent decrease in the net positive surface charge density of the amphiphilic monoliths. The cationic C18-monoliths exhibited reversed-phase chromatography (RPC) behavior toward non-polar solutes (e.g., alkyl benzenes), which parallels that observed with octadecyl-silica (ODS) monoliths. On the other hand, the amphiphilic stationary phases exhibited both non-polar and polar interactions toward slightly polar solutes such as anilines and PTH-amino acids. CEC retention factor k* and velocity factor k*e, which reflects the contribution of the electrophoretic mobility, were evaluated for charged solutes such as anilines and proteins.

Electrically driven microseparation methods for pesticides and metabolites. II: on-line and off-line preconcentration of urea herbicides in capillary electrochromatography.

Capillary electrochromatography (CEC) was introduced to the separation of nine important urea herbicides using octadecyl-silica (ODS) capillary columns that were specially designed to allow the realization of a relatively strong electroosmotic flow (EOF) and, in turn, fast separations. The ODS stationary phase was intentionally prepared to have a low surface coverage in octadecyl ligands in order to ensure a strong EOF. This ODS stationary phase of low surface coverage exhibited the usual reversed-phase chromatographic behavior as was manifested by the linearity of plots of log kappa versus the percent organic modifier in the mobile phase. The nature of the organic modifier of the mobile phase influenced the order of elution as well as the separation efficiency of the nine urea herbicides. Mobile phases containing acetonitrile yielded higher separation efficiency (by a factor of 1.5) than methanol-containing mobile phases. This was attributed to the higher mass transfer resistances of the solute in and out of the pores in the presence of the more viscous methanol-containing mobile phases. Due to the relatively strong affinity of the urea herbicides to the ODS stationary phase, on-line preconcentration consisting of prolonged injections allowed the determination of 10(-5) M urea herbicide samples using a UV detector without sacrificing separation efficiency. This was further decreased to 10(-7) M when the prolonged injection was preceded by the injection of a plug of water. The plug of water (the more retentive mobile phase) brought about an enhanced accumulation of the dilute samples into a narrow band at the inlet of the CEC column. When this on-column sample enrichment approach was combined with an off-line sample preconcentration step, which consisted of a solid-phase extraction process, ultra dilute samples of 10(-10) M (0.1 ppb) could be detected.

Raman Spectroscopic Characterization of RP-18-Type Chemically Bonded Stationary Phases for Liquid Chromatography

Abstract This study is the first Raman spectroscopic characterization of conventional chemically bonded liquid chromatographic (LC) stationary phases of the RP-18 type using the high-power Nd:WV04 neodymium laser. Raman spectra were obtained for octadecyl (C18) chemically bonded silica-based stationary phases, as well as for silica, aminopropyl (NH2), cyanopropyl (CN), diol (OH), octyl (C8), and methyl (C1) phases for comparison. This study demonstrates that Raman spectroscopy using the high-power neodymium laser can be used to study RP-18-type LC stationary phases and to quantitate the density of coverage of the silica matrix with octadecyl ligands. The paper presents the experimental setup and conditions usedto obtain Raman spectra of commercial RP-18-type chemically bonded stationary phases and examines the spectroscopic similarities and differences observed for different bonded ligands typically used in reversed-phase and normal-phase LC separations.