Physico-chemical characterization of MCM-41 silica spheres made by the pseudomorphic route and grafted with octadecyl chains

This work reports on the first comprehensive characterization of octadecyl (C(18)) modified MCM-41 silica spheres, prepared via the pseudomorphic route, followed by grafting with mono- or trifunctional octadecyl (C(18)) alkyl chains and endcapping with hexamethyldisilazane. Small angle X-ray scattering (SAXS), nitrogen adsorption-desorption and scanning electron microscopy (SEM) measurements were performed to obtain information about the MCM-41 pore structure, surface properties and morphological features. The degree of grafting and cross-linking of the silanes were determined by (29)Si magic angle spinning NMR spectroscopy, while FTIR and (13)C NMR were employed to study the conformational behavior of the surface-immobilized alkyl chains. The SAXS pattern proved the existence of a hexagonal mesopore arrangement for both the ungrafted and the grafted MCM-41 silica spheres. In addition, there is evidence of some long-range distortion in the pore structure. SEM measurements revealed the same morphological features for the parent silica and the MCM-41 silica spheres before and after C(18) grafting. The achieved surface loading for the MCM-41 material is rather low. It was also shown that a substantial amount of the accessible surface silanol groups is endcapped by trimethylsilane which in turn results in a very low surface coverage due to the octadecyl chains. The nitrogen sorption studies provided values for the surface area, total pore volume and pore diameter which are very typical for mesoporous materials. The reduction in surface area and total pore volume upon surface grafting is related to the binding of trimethylsilane in the interior of the pores, while due to the spatial restrictions octadecyl chains are primarily attached near the pore entrance. The experimental FTIR and (13)C NMR data point to a very low conformational order of the C(18) chains which is in accordance with the observed low surface coverage and the resulting spatial freedom for these surface-immobilized alkyl chains.     

Adsorption of codeine on hydrophilic silica and silica surface modified by hydrophobic groups in the presence of electrolytes

The adsorption of codeine from aqueous solution onto colloidal silica and silica surface-modified with chemiadsorbed octadecyl dimethyl silane (ODDMS) or dimethyl silane (DMS) groups was studied in the presence of neutral electrolytes at different pH values. From codeine-hydrochloride solutions codeine cations are strongly bound to negatively charged silica surfaces. Inorganic salts (NaCl, NaNO₃) reduce the adsorption of the organic cation. On silica modified by ODDMS (10% of surface silanol groups are occupied), codeine cations are adsorbed to a higher extent at pH 6, while at pH 8 the adsorbed amounts are lower than on the bare silica surface. Neutral electrolytes reduce codeine adsorption on the ODDMS modified silica. On the hydrophobic silica, completely covered by DMS groups, codeine adsorption is considerably lower than on the bare silica, but neutral salts increase the adsorption. The adsorption of codeine is compared with the adsorption of aggregating surfactant ions. Common and different features of their interactions with silica surfaces are outlined.     

Examination of the surface heterogeneity of reversed-phase packing materials with solvent adsorption

The adsorption isotherms of acetonitrile, ethanol, 2-propanol, and THF were measured using frontal analysis on six columns packed with octadecyl RP stationary phase. The effect of the bonding density of the end-capped octadecyl bonded phase on the adsorption properties was measured. Adsorption isotherm data were collected from aqueous solutions of the four organic modifiers. The isotherm model for solvent adsorption was selected using two independent parameter estimation methods, the regression analysis and adsorption energy distribution. The fitted isotherm parameters were tested by modeling of overloaded elution bands with the aid of the equilibrium-dispersive model of chromatography. The surface heterogeneity estimations and the effect of the silanol groups on the adsorption of solvents were based on those data.     

Thermodynamics of adsorption of binary aqueous organic liquid mixtures on a RPLC adsorbent

The surface excess adsorption isotherms of organic solvents commonly used in RPLC with water as co-eluent or organic modifiers (methanol, ethanol, 2-propanol, acetonitrile and tetrahydrofuran) were measured on a porous silica surface derivatized with chlorotrimethylsilane (C1-silica with 3.92 micromol C1 groups per m2 of SiO2), using the dynamic minor disturbance method. The 5 microm diameter particles were packed in a 150 mm x 4.6 mm column. The isotherm data were derived from signals resulting from small perturbations of the equilibrium between the aqueous-organic solutions and the adsorbent surface. The partial molar surface area of the adsorbed components were assumed to be the same as those of the pure components. The difference sigma-sigmai* between the surface tensions of the adsorbed mixtures and that of the pure liquids was measured as a function of the organic modifier molar fraction. A simple and unique convention for the position of the Gibbs dividing surface was proposed to delimit the Gibbs's adsorbed phase and the bulk liquid phase. The activity coefficients of the organic modifiers and of water and their thermodynamic equilibrium constants between the two phases were measured. The strong non-ideal behavior of the adsorbed phase is mostly accounted for by the surface heterogeneity. Some regions of the surface (bonded -Si(CH3)3 moieties) preferentially adsorb the organic compound while the regions close to unreacted silanols preferentially adsorb water.     

Effect of the endcapping of reversed-phase high-performance liquid chromatography adsorbents on the adsorption isotherm

The retention mechanisms of n-propylbenzoate, 4-t ert-butylphenol, and caffeine on the endcapped Symmetry-C(18) and the non-endcapped Resolve-C(18) are compared. The adsorption isotherms were measured by frontal analysis (FA), using as the mobile phase mixtures of methanol or acetonitrile and water of various compositions. The isotherm data were modeled and the adsorption energy distributions calculated. The surface heterogeneity increases faster with decreasing methanol concentration on the non-endcapped than on the endcapped adsorbent. For instance, for methanol concentrations exceeding 30% (v/v), the adsorption of caffeine is accounted for by assuming three and two different types of adsorption sites on Resolve-C(18) and Symmetry-C(18), respectively. This is explained by the effect of the mobile phase composition on the structure of the C(18)-bonded layer. The bare surface of bonded silica appears more accessible to solute molecules at high water contents in the mobile phase. On the other hand, replacing methanol by a stronger organic modifier like acetonitrile dampens the differences between non-endcapped and endcapped stationary phase and decreases the degree of surface heterogeneity of the adsorbent. For instance, at acetonitrile concentrations exceeding 20%, the surface appears nearly homogeneous for the adsorption of caffeine.     

Adsorption mechanism in reversed-phase liquid chromatography. Effect of the surface coverage of a monomeric C18-silica stationary phase

The effect of the bonding density of the octadecyl chains onto the same silica on the adsorption and retention properties of low molecular weight compounds (phenol, caffeine, and sodium 2-naphthalene sulfonate) was investigated. The same mobile phase (methanol:water, 20:80, v/v) and temperature (T = 298 K) were applied and two duplicate columns (A and B) from each batch of packing material (neat silica, simply endcapped or C1 phase, 0.42, 1.01, 2.03, and 3.15 micromol/m2 of C18 alkyl chains) were tested. Adsorption data of the three compounds were acquired by frontal analysis (FA) and the adsorption energy distributions (AEDs) were calculated using the expectation-maximization method. Results confirmed earlier findings in linear chromatography of a retention maximum at an intermediate bonding density. From a general point of view, the saturation capacity of the adsorbent tends to decrease with increasing bonding density, due to the vanishing space intercalated between the C18 bonded chains and to the decrease of the specific surface area of the stationary phase. The equilibrium constants are maximum for an intermediary bonding density (approximately 2 micromol/m2). An enthalpy-entropy compensation was found for the thermodynamic parameters of the isotherm data. Weak equilibrium constants (small deltaH) and high saturation capacities (large deltaS) were observed at low bonding densities, higher equilibrium constants and lower saturation capacities at high bonding densities, the combinations leading to similar apparent retention in RPLC. The use of a low surface coverage column is recommended for preparative purposes.     

Separation Mechanism of Copolymers from Styrene and Methyl Methacrylate According to Composition by Liquid Adsorption Chromatography

Abstract

Silica gel and a mixture of chloroform and ethanol were used as the stationary and the mobile phases, respectively. At the isocratic elution mode, the copolymers tended to adsorb on the column with increasing MMA content in the copolymers, with increasing column temperature, and with decreasing ethanol content in the mobile phase. The copolymers appeared always at the position proportional to the interstitial volume in the column, otherwise they adsorbed on the column. The equilibrium distribution of the copolymers between the mobile phase and the stationary phase cannot be considered in this system. Hydrogen bonding of carbonyl groups in MMA units of the copolymers to silanol groups on the surface of silica gel was considered to be the main interaction between the copolymers and the adsorbent. The hydrogen bonding increases with increasing the number of carbonyl groups per unit surface of copolymer coil in solution and with increasing free silanol groups on the silica surface. Ethanol in the stationary phase controls the content of the free silanol groups on the surface and is controlled by the content of ethanol in the mobile phase in addition to column temperature. This phenomena can be explained by introducing the term of the adsorption energy of a copolymer segment with the silica surface. The adsorption energy is proportional to the strength of the hydrogen bonding. Above the critical adsorption energy which is defined to be equal to the dissolution energy of the copolymer to the mobile pahse, the copolymers adsorb on the surface of silica gel and the desorption of the copolymers advances when the adsorption energy approaches to the critical adsorption energy. No adsorption of the copolymers is possible when the adsorption energy is equal or below the critical adsorption energy.     

The versatile surface properties of poly(cyclopentadiene)-modified silica particles (PCPD–silica): XPS and electrokinetic studies

Surface properties of poly(cyclopentadiene)–silica hybrid particles (PCPD–silica) were studied by means of XPS and electrokinetic measurements. The surfaces of PCPD–silica particles exhibit two different areas with different properties: bare silica holes and PCPD patches. The PCPD chains contain different functional groups such as alcohol and carbonyl groups that were identified by XPS. The PCPD chains are grafted covalently onto the silica surface via Si–O–C bonds created by the reaction of silanol groups and active PCPD chains. The amount of Si–O–C was examinated by means of XPS. The Brønsted acidity of the residual silanol groups was determined by means of electro-kinetic measurements. It was found that the pK _a values of the residual silanol groups increase with increasing polymer content on the particle surface. The surface acceptor strengths of the hybrid particles in non-aqueous liquids were investigated by the solvatochromic indicator bis(1,10-phenanthroline)-cis-dicyano-iron-II in 1,2-dichloroethane.     

New Insights into the Effects of Tetrahydrofuran and Dioxane on the Selectivity of Ternary Eluent Compositions in RP-HPLC Systems

The present paper discusses the tendencies in the retention changes of a diverse set of organic model compounds on HPLC C18 stationary phases in aqueous ternary eluent mixtures containing tetrahydrofuran or 1,4-dioxane, and one short chain aliphatic alcohol (ethanol, n-propanol or isopropanol). The set of compounds consisted of steroid and non-steroid molecules with different hydrogen bond donor and/or acceptor abilities. Every eluent mixture contained 75 V/V% water and 25 V/V% organic solvent(s). The composition of the mixture was changed in 5 V/V% steps, starting with the binary alcohol–water mixtures and finishing with the binary ether–water mixtures. The results show clearly the dependency of retention times on the eluent composition, the size of the molecules, and the occurence of the hydrogen bond donor/acceptor groups. The isopropanol–tetrahydrofurane–water mixtures resulted in selective changes in the retention times of the compounds with acidic groups or with other non-acidic OH or NH protons in the neighborhood of electron-withdrawing groups. Every compound has shown elevated retention times in the isopropanol–dioxane–water, n-propanol–tetrahydrofuran–water, or n-propanol–dioxane–water mixtures. Clear trends could not be observed in the eluents with ethanol. The probable reason for the retention enhancement is the adsorption of the organic components of the mobile phase on the surface of the stationary phase. The different effects of the alcohols may originate from the interaction of their varying aliphatic alkyl chains with the C18 chains. This phenomenon may result in different availability of the C18 chains for dioxane, tetrahydrofuran and the model compounds.     

Fast methods for screening of trichothecenes in fungal cultures using gas chromatography-tandem mass spectrometry

The excess adsorption isotherms of acetonitrile, methanol and tetrahydrofuran from water on reversed-phase packings were studied, using 10 different columns packed with C1-C6, C8, C10, C12, and C18 monomeric phases, bonded on the same type of silica. The interpretation of isotherms on the basis of the theory of excess adsorption shows significant accumulation of the organic eluent component on the adsorbent surface on the top of "collapsed" bonded layer. The accumulated amount was shown to be practically independent of the length of alkyl chains bonded to the silica surface. A model that describes analyte retention on a reversed-phase column from a binary mobile phase is developed. The retention mechanism involves a combination of analyte distribution between the eluent and organic adsorbed layer, followed by analyte adsorption on the surface of the bonded phase. A general retention equation for the model is derived and methods for independent measurements of the involved parameters are suggested. The theory was tested by direct measurement of analyte retention from the eluents of varied composition and comparison of the values obtained with those theoretically calculated values. Experimental and theoretically calculated values are in good agreement.     

Chemical Mechanism of the Solid-Phase Extraction of Metal Complexes: Barium Complexes with Crown Ethers

The adsorption of barium complexes of dibenzo-18-crown-6 (DB18C6) and dicyclohexano-18-crown-6 (DCH18C6) ethers on alkylated silica gel in the presence of sodium dodecylsulfonate was studied. The adsorbent capacity for the barium complex of DCH18C6 was higher than that for the complex of DB18C6 by a factor of about 4. Depending on the proton-acceptor ability of the adsorbate, the surface layer of alkyl radicals and residual silanol groups behaves as a solid surface or a liquid phase. In the latter case, a supramolecular cavity complementary to the adsorbate is formed in the surface phase. Thus, alkylated silica gel undergoes self-organization with regard to the properties of the adsorbate. This hypothesis explains the unusual adsorption of barium complexes.     

在线固相氧化物吸附-火焰原子吸收法测定痕量银

基于硅胶表面对碱性体系中新生成的氧化银(Ag2O)的有效吸附, 建立了流动注射-固相氧化物分离富集-火焰原子吸收法测定痕量银的方法. 当银以氧化物的形式被滞留在硅胶固相表面时, 硅胶表面的硅醇基和表面电荷有利于反应体系中新生成的Ag2O胶状沉淀的吸附, 将收集的沉淀用HNO3(10%, 体积分数)洗脱后用火焰原子吸收测定. 当进样体积为5.4 mL时, 测得的富集系数为25.5, 检出限为0.6 μg/L, 采样频率为50次/h, 线性范围为2~150 μg/L, 相对标准偏差(RSD)为2.0%(40 μg/L, n=11). 将该法用于自来水、河水、井水、雪水和山泉水中银含量的测定, 加标回收率分别为93.3%, 89.5%, 96.6%, 108.4%和102.8%.     

Effect of the density of the C(18) surface coverage on the adsorption mechanism of a cationic compound and on the silanol activity of the stationary phase in reversed phase liquid chromatography

RPLC columns with different surface coverages (a C(1) endcapped column with a bonding density of 3.92 micromol/m(2) and four C(18)-bonded, endcapped columns, with octadecyl chain densities of 0.42, 1.01, 2.03, and 3.15 micromol/m(2)) were used to investigate the effects of the density of the surface coverage of RPLC columns on the adsorption mechanism of a cationic compound, amitriptyline chloride, and on the silanol activity of these columns. The mobile phases used were acetonitrile-water (30/70, v/v) solutions, buffered at either pH 2.7 or pH 6.9. At pH 2.7, the residual silanol groups are not ionized. At pH 6.9, some of these groups are ionized and these surface anions can strongly interact with the cationic compound. The adsorption isotherms were measured by frontal analysis (FA) at pH 2.7 and by frontal analysis by characteristic points (FACP) at pH 6.9, because the very high retention observed at neutral pH made FA measurements excessively long and poorly accurate. The adsorption energy distributions (AEDs) were calculated when possible, according to the expectation-maximization (EM) algorithm. A bimodal and a trimodal energy distribution were found for all the columns at pH 2.7 and 6.9, respectively. The third site measured at pH 6.9 was attributed to the strong ion-exchange interactions between the ionized silanol groups and the amitriptylinium cation. The contribution of the ionized silanol groups to the overall retention is maximum for the phases with intermediary bonding densities (1.01 and 2.03 micromol/m(2)). The peak tailing is most pronounced for the lowest (C(1) column) and the highest (3.15 micromol/m(2)) surface coverages.     

Polymer modification of colloidal particles by spontaneous polymerization of surface active monomers

Adsorption and spontaneous polymerization of head- or tail-type surface active monomers having long methylene chains on colloidal silica and δ-alumina were investigated. Both head-type and tail-type ammonium monomers on silica in chloroform or tetrahydrofuran had the maximum adsorption on the respective adsorption isotherm. Above the monomer concentration giving the maximum adsorption, it was observed that the monomer formed micelles or clusters in bulk solution with removal of adsorbed water molecules from the silica surface. At the monomer concentration giving the maximum adsorption, heating the silica suspension containing the monomer at 40°C or 60°C in tetrahydrofuran or chloroform solution resulted in spontaneous polymerization. The composite particles formed by polymerization were observed to have many spots consisting of polymer on the surface. Therefore, it is suggested that the monomers are concentrated by micelle-like aggregation on the silica surface and consecutively spontaneous polymerization takes place. Adsorption of an anion-type monomer having a carboxyl group on δ-alumina, which exhibited a positive ζ potential in neutral aqueous solution, was higher than that on colloidal silica, but did not spontaneously polymerize on alumina. Received: 13 June 1998 Accepted in revised form: 19 August 1998     

Energetics of protein adsorption on amine-functionalized mesostructured cellular foam silica

The energetics of lysozyme adsorption on aminopropyl-grafted MCF silica (MCF-NH2) are compared to the trends observed during lysozyme adsorption on native MCF silica using flow microcalorimetry (FMC). Surface modification on MCF silica affects adsorption energetics significantly. All thermograms consist of two initial exothermic peaks and one later endothermic peak, but the heat signal trends of MCF-NH2 are opposite from those observed for adsorption onto native MCF silica in salt solutions of sodium acetate and sodium sulfate. At low ionic strength (0.01 M), LYS adsorption onto MCF-NH2 was accompanied by a large exotherm followed by a desorption endotherm. With increasing ionic strength (0.1 and 3.01 M), the magnitude of the thermal signal decreased and the total process became less exothermic. Also a higher protein loading of 14 μmol g(-1) was obtained at low ionic strength in batch adsorption isotherm measurements. Taken together, the FMC thermograms and batch adsorption isotherms reveal that MCF-NH2 has the nature of an ion exchange adsorbent, even though lysozyme and the aminopropyl ligands have like net charges at the adsorption pH. Reduced electrostatic interaction, reduced Debye length, and increased adsorption-site competition attenuate exothermicity at higher ionic strengths. Thermograms from flow microcalorimetry (FMC) give rich insight into the mechanisms of protein adsorption. A two-step adsorption mechanism is proposed in which negatively charged surface amino acid side chains on the lysozyme surface make an initial attachment to surface aminopropyl ligands by electrostatic interaction (low ionic strength) or van der Waals interaction (high ionic strength). Secondary attachments take place between protruding amino acid side chains and silanol groups on the silica surface. The reduced secondary adsorption heat is attributed to the inhibitory effect of the enhanced steric barrier of aminopropyl group on MCF silica.     

Adsorption of midmolecular peptides by fullerene modified silica gel

The adsorption properties of raw and processed silica gels and of silica gels modified with fullerene (fullerene-silica gel nanosystems) toward serum midmolecular peptides of ischemic origin were examined. A high adsorption capacity of the nanosorbents was found. The influence of fullerenes on the condition of silica gel was studied by solid-state NMR, and an increase in the silanol fraction at the adsorbent surface was demonstrated. It was shown that presence of fullerene C₆₀ in nanosorbents enables oxidation reaction of the adsorbed peptides, i.e., sorption of metabolites.     

A study of the alumina-silica gel adsorbent for the removal of silicic acid from geothermal water: increase in adsorption capacity of the adsorbent due to formation of amorphous aluminosilicate by adsorption of silicic acid

Two kinds of adsorbents (Si adsorbent and Al adsorbent) for the removal of silicic acid from geothermal water to retard the formation of silica scales were prepared using silicic acid contained in geothermal water. The Si adsorbent was prepared by evaporating geothermal water, and the Al adsorbent was prepared by evaporating geothermal water after the addition of aluminum chloride. The specific surface area of the Si adsorbent was small and it's adsorption capacity of silicic acid was low. Although the specific surface area of the Al adsorbent was also small, it was significantly increased by the adsorption of silicic acid and it's adsorption capacity was high. Based on the change in the local structure of aluminum ion by the adsorption of silicic acid, the Al adsorbent was considered to be silica particles covered with crystalline aluminum hydroxide. Moreover, it was concluded that the increase in the specific surface area of the Al adsorbent and the decrease in the zeta potential were due to the formation of an amorphous aluminosilicate with a large surface area and a negative charge (one 4-coordinated Al) by the reaction between aluminum ions and silicic acids.     

An FTIR study of the adsorption of surfactants on silica

The absorption of cetyltrimethyl ammonium bromide onto silica was studied by FTIR as an example of the interaction of cationic surfactants with surfaces of medium polarity. It was found that the free silanol groups of the silica interacted strongly with the surfactant and that the methylene group adsorption bands varied with coverage in both frequency and width. These results could be interpreted in terms of chemisorption of a first layer of surfactant followed by physisorption of subsequent layers, or in terms of the inhomogeneity of the silica surface.     

Chemistry of aqueous silica nanoparticle surfaces and the mechanism of selective peptide adsorption

Control over selective recognition of biomolecules on inorganic nanoparticles is a major challenge for the synthesis of new catalysts, functional carriers for therapeutics, and assembly of renewable biobased materials. We found low sequence similarity among sequences of peptides strongly attracted to amorphous silica nanoparticles of various size (15-450 nm) using combinatorial phage display methods. Characterization of the surface by acid base titrations and zeta potential measurements revealed that the acidity of the silica particles increased with larger particle size, corresponding to between 5% and 20% ionization of silanol groups at pH 7. The wide range of surface ionization results in the attraction of increasingly basic peptides to increasingly acidic nanoparticles, along with major changes in the aqueous interfacial layer as seen in molecular dynamics simulation. We identified the mechanism of peptide adsorption using binding assays, zeta potential measurements, IR spectra, and molecular simulations of the purified peptides (without phage) in contact with uniformly sized silica particles. Positively charged peptides are strongly attracted to anionic silica surfaces by ion pairing of protonated N-termini, Lys side chains, and Arg side chains with negatively charged siloxide groups. Further, attraction of the peptides to the surface involves hydrogen bonds between polar groups in the peptide with silanol and siloxide groups on the silica surface, as well as ion-dipole, dipole-dipole, and van-der-Waals interactions. Electrostatic attraction between peptides and particle surfaces is supported by neutralization of zeta potentials, an inverse correlation between the required peptide concentration for measurable adsorption and the peptide pI, and proximity of cationic groups to the surface in the computation. The importance of hydrogen bonds and polar interactions is supported by adsorption of noncationic peptides containing Ser, His, and Asp residues, including the formation of multilayers. We also demonstrate tuning of interfacial interactions using mutant peptides with an excellent correlation between adsorption measurements, zeta potentials, computed adsorption energies, and the proposed binding mechanism. Follow-on questions about the relation between peptide adsorption on silica nanoparticles and mineralization of silica from peptide-stabilized precursors are raised.