Adsorption of organic molecules on silica surface

The adsorption behaviour of various organic adsorbates on silica surface is reviewed. Most of the structural information on silica is obtained from IR spectral data and from the characteristics of water present at the silica surface. Silica surface is generally embedded with hydroxy groups and ethereal linkages, and hence considered to have a negative charged surface prone to adsorption of electron deficient species. Adsorption isotherms of the adsorbates delineate the nature of binding of the adsorbate with silica. Aromatic compounds are found to involve the pi-cloud in hydrogen bonding with silanol OH group during adsorption. Cationic and nonionic surfactants adsorb on silica surface involving hydrogen bonding. Sometimes, a polar part of the surfactants also contributes to the adsorption process. Styryl pyridinium dyes are found to anchor on silica surface in flat-on position. On modification of the silica by treating with alkali, the adsorption behaviour of cationic surfactant or polyethylene glycol changes due to change in the characteristics of silica or modified silica surface. In case of PEG-modified silica, adsolubilization of the adsorbate is observed. By using a modified adsorption equation, hemimicellization is proposed for these dyes. Adsorptions of some natural macromolecules like proteins and nucleic acids are investigated to study the hydrophobic and hydrophilic binding sites of silica. Artificial macromolecules like synthetic polymers are found to be adsorbed on silica surface due to the interaction of the multifunctional groups of the polymers with silanols. Preferential adsorption of polar adsorbates is observed in case of adsorbate mixtures. When surfactant mixtures are considered to study competitive adsorption on silica surface, critical micelle concentration of individual surfactant also contributes to the adsorption isotherm. The structural study of adsorbed surface and the thermodynamics of adsorption are given some importance in this review.     

Adsorption and protection of plasmid DNA on mesoporous silica nanoparticles modified with various amounts of organosilane

Ordered MCM-41-type mesoporous silica nanoparticles (MSNs) with pore size of 2.6 nm were synthesized and were further modified with various amounts of 3-aminopropyltriethoxysilane (APTES), respectively, by a direct co-condensation method. These amine functionalized mesoporous silica nanoparticles (Am-MSNs) were employed to complex with plasmid DNA (pDNA) to study their adsorption and protection capacities. The results demonstrate the MSNs functionalized with aminopropyl groups present advanced adsorption capacities for pDNA immobilization. And Am-MSNs with high APTES amount lead to high amount of pDNA adsorption. Further investigation of pDNA protection shows that Am-MSNs with moderate APTES amount could completely protect pDNA from enzymatic degradation, while those with smaller and/or higher amount of APTES could partially provide protection of pDNA.     

Adsorption of DNA into mesoporous silica

In these experiments, double-stranded, linear DNA sequences were adsorbed into the pores of spherically shaped acid-prepared mesoporous silica (APMS). The lengths of the sequences were either 760 base pairs or 2000 base pairs. DNA adsorption into the interior of the mesoporous material was confirmed using confocal microscopy of sequences containing fluorescently labeled DNA molecules. Additional characterization with N(2) physisorption and powder X-ray diffraction supported this finding. The extent of adsorption was measured at various concentrations using UV-visible spectrophotometry to establish adsorption isotherms. APMS alone adsorbed a negligible amount of DNA; however, exchanging divalent cations such as Mg(2+) and Ca(2+) into the pores of APMS prior to DNA uptake was found to cause a significant amount of DNA to be adsorbed. Using Na(+) caused a lower amount of DNA to be adsorbed. DNA adsorption was also dependent on the pore diameter of APMS. Adsorption increased upon expansion of the pore size of the metal ion-exchanged material from 34 to 54 A; however, no additional uptake was measured by further increasing the pore size to 100 A. The amount of DNA adsorbed could also be significantly increased by using (aminopropyl)triethoxysilane to covalently link ammonium ions to the surface. Postsynthetic modification of the silica surface with aminopropyl groups increased the maximum DNA adsorption to 15.7 microg/mg silica, for materials with pore diameters of 100 A, which is 2 to 3 times more adsorbed DNA than for metal ion-exchanged material. This indicated that DNA binds more strongly in the presence of the ammonium group compared to the metal counterions. Finally, calculation and comparison of Freundlich and Langmuir constants for these adsorption processes indicate that intermolecular interactions between the DNA molecules within the pores are significant when the effective pore diameter is small, including materials with larger pores that were modified with organosilane.     

Adsorption of catechol on a wet silica surface: density functional theory study

Marine mussel proteins adhere permanently to diverse wet surfaces via their catechol (1, 2-dihydroxybenzene) functionality. To elucidate the molecular mechanism underlying this water-resistant adhesion, we performed density functional theory calculations for the competitive adsorption of catechol and water on a wet silica surface. Results show the energetic spontaneity of the reaction; catechol displaces water molecules and adheres directly to the surface. This result was subsequently corroborated by our molecular dynamics simulation.     

Adsorption kinetics of p-nitrobenzenethiol self-assembled monolayers on a gold surface

The adsorption kinetics of octadecanethiol (ODT) and p-nitrobenzenethiol (NBT) from ethanol solutions has been studied by means of contact angle, optical ellipsometry, angle-resolved X-ray photoelectron spectroscopy (ARXPS), and grazing angle attenuated total reflection Fourier transform infrared (FTIR) measurements. ODT data were used as a reference for the kinetics studies of film growth. The growth of self-assembled monolayers from dilute solutions follows Langmuir isotherm adsorption kinetics. A saturated film is formed within 5 h after immersion in solutions of concentrations ranging from 0.0005 to 0.01 mM. The density of the monolayer depends on the concentration of the solution.     

Adsorption kinetics of carcinogens to DNA liquid crystalline gel beads

Adsorption behaviors of acridine orange (AO) and biphenyl (BP) to DNA liquid crystalline gel (LCG) beads in aqueous dispersing solution have been studied theoretically and experimentally. A theoretical consideration based on nonequilibrium thermodynamics predicted that the time course of the adsorption process is expressed with a scaled equation, and a scaled number of adsorbed carcinogen molecules ? is expressed with the square root of a scaled immersion time t, ? proportional, variant square root t at early stage, whereas it is expressed with a power law function 1 - ? proportional, variant (te - t)3/2 for ?0 > 1 and an exponential equation ?0 - ? proportional, variant e-t/alpha tau0 for ?0 > 1 at later stages of adsorption. Here, ?0 is the ratio of the initial number of carcinogen molecules in the dispersing solution to the number of the sites of adsorption of carcinogen molecules in the beads, te is the scaled equilibrium time of adsorption, tau0 is a time constant for adsorption, and alpha is a constant. Observed adsorption processes for AO were well expressed by the predicted ones, and the fitting parameters ?0 and tau0 increased with increasing cobalt chloride concentration CCo used for preparation of the beads, and both saturated above CCo > or = 400 mM for the adsorption of AO, whereas the adsorption processes for BP were expressed with the square root function. These results indicate that (1) the adsorption process at early stage is explained by diffusion-limited binding of the carcinogen molecules to DNA beads, and the time range of the early stage depends on the solubility (the solubility of AO in water is high whereas that of BP is low); and (2) the process at later stages depends on the balance of the numbers of adsorption sites and carcinogen molecules.     

Adsorption properties of highly dispersed silica with a partially hydrophobic surface

Highly dispersed silica samples with different degrees of substitution of silanol groups by trimethylsilyl groups are obtained by the gas-phase modification method. The adsorption of vitamins B1, B6, and E on initial and modified silica samples is studied. It is shown that the modified adsorbents with degrees of substitution of silanol groups up to 40% exhibit higher affinity to vitamin molecules; in this case, adsorption properties of the modified silica samples depend on the nature of the adsorbate and the number of grafted groups.     

Adsorption of biogenic amines on albumin-modified silica surface

The adsorption of biogenic amines, tryptamine and tyramine, from aqueous solutions on the surface of finely dispersed silica modified by the adsorption of bovine serum albumin is studied depending on pH and adsorbate concentration. Silica surface modification with albumin is shown to widen the pH range of amine adsorption from aqueous solutions.     

Adsorption of organic liquids on alkaline earth-metal modified silica

Summary Adsorption properties of alkaline earth-metal modified silica beads were investigated by the gas-solid chromatography (GSC) method. Silica beads, obtained from colloidal material, were characterized by their surface areas, crystallinity and amount of sorbed alkaline earth cations. Retentions of several aliphatic, alicyclic, chlorinated, and aromatic compounds were measured in the temperature range from 373 to 453 K.The gas/solid partition coefficients, K₅, and the related thermodynamic functions at zero surface coverage were determined. The results show that the specific surface areas of modified silica samples remain practically constant, whereas the modification leads to a decrease of silica surface heterogeneity.     

Adsorption of poly(ethyleneimine) on silica surfaces: effect of pH on the reversibility of adsorption

The role of polymer charge density in the kinetics of the adsorption and desorption, on silica, of the polyelectrolyte poly(ethyleneimine) (PEI) was investigated by stagnation-point flow reflectometry. In the first series of experiments, PEI solutions were introduced at the same ionic strength and pH as the background solvent. It was found that the adsorbed amount of PEI increased by increasing pH. In the second series of investigations, several PEI solutions with ascending pH were introduced consecutively into the cell. In these cases, a stepwise buildup of the adsorbed amount was observed and the "final" adsorbed amounts were observed to be roughly equal with the adsorbed amounts of the first series of measurements at the same pH. Finally, adsorption/desorption experiments were performed where the preadsorption of PEI was followed by the introduction of PEI solutions of descending pH. No desorption was detected when the pH changed from pH = 9.7 to pH = 5.8. However, when there was a 9.7 --> 3.3 or 5.8 --> 3.3 decrease in the pH, the kinetic barriers of desorption seemed to completely disappear and roughly the same adsorbed amount as in the first series of experiments at pH = 3.3 was quickly attained by desorption of the PEI. This study reveals the high impact of pH, affecting parameters such as charge density of the surface and polyelectrolyte as well as the structure of the adsorbed macromolecules, on the desorption properties of weak polyelectrolytes. The observed interfacial behavior of PEI may have some important consequences for the stability of alternating polyelectrolyte multilayers containing weak polyelectrolytes.     

Adsorption of plasmid DNA on anion exchange chromatography media

Anion exchange chromatography (AEC) is a useful and effective tool for DNA purification, but due to average pore sizes between 40 and 100 nm most AEC resins lack truly useful binding capacities for plasmid DNA (pDNA). Equilibrium binding capacities and uptake kinetics of AEC media including conventional media (Source 30 Q, Q Sepharose HP), a polymer grafted medium (Fractogel EMD DEAE (M)), media with large pores (Celbeads DEAE, PL SAX 4000 A 30 microm) and a monolithic medium (CIM-DEAE) were investigated by batch uptake or shallow bed experiments at two salt concentrations. Theoretical and experimental binding capacities suggest that the shape of the pDNA molecule can be described by a rod with a length to diameter ratio of 20:1 and that the molecule binds in upright position. The arrangement of DNA like a brush at the surface can be considered as entropy driven, kind of self-assembly process which is inherent to highly and uniformly charged DNA molecules. The initial phase of adsorption is very fast and levels off, associated with a change in mass transfer mechanism. Feed concentrations higher than 0.1 mg/mL pDNA pronounce this effect. Monolithic media showed the fastest adsorption rate and highest binding capacity with 13 mg pDNA per mL.     

Adsorption of plasmid DNA on ceramic hydroxyapatite chromatographic materials

The adsorption of plasmid DNA onto two different types of ceramic hydroxyapatite beads with a particle diameter of 20 μm, namely Ceramic Hydroxyapatite Type II and the Type III, which is not commercially available, were investigated. Type II and the Type III have a pore diameter of 80 and 240 nm, respectively. Equilibrium and dynamic binding capacity for a 4.9 kbp model plasmid on Ceramic Hydroxyapatite Type II and Type III were enhanced by addition of NaCl to the adsorption buffer. This result indicates that the adsorption mechanism cannot be solely explained by electrostatic interaction. The affinities of plasmid DNA for Ceramic Hydroxyapatite Type II (with a K(D) of ≈0.005 mg/mL) and to Hydroxyapatite Type III (with a K(D) of ≈0.045 mg/mL) were not affected by NaCl, whereas the binding capacity was. This observation corroborates the assumption that a change of the shape of the plasmid molecule is affected and could be the reason for increased binding capacity with salt. The maximal binding capacity shows that at least a part of the CHT II bead must be accessible for the plasmid, whereas CHT III can be saturated with the plasmid. In both cases, an extremely hindered transport takes place.     

Influence of natural organic matter on the deposition kinetics of extracellular polymeric substances (EPS) on silica

The influence of humic acid and alginate, two major components of natural organic matter (NOM), on deposition kinetics of extracellular polymeric substances (EPS) on silica was examined in both NaCl and CaCl(2) solutions over a wide range of environmentally relevant ionic strengths utilizing a quartz crystal microbalance with dissipation. Deposition kinetics of both soluble EPS and bound EPS extracted from four bacterial strains with different characteristics was investigated. EPS deposition on humic acid-coated silica surfaces was found to be much lower than that on bare silica surfaces under all examined conditions. In contrast, pre-coating the silica surfaces with alginate enhanced EPS deposition in both NaCl and CaCl(2) solutions. More repulsive electrostatic interaction between EPS and surface contributed to the reduced EPS deposition on humic acid-coated silica surface. The trapping effect induced by the rough alginate layer resulted in the greater EPS deposition on alginate-coated surfaces in NaCl solutions, whereas surface heterogeneities on alginate layer facilitated favorable interactions with EPS in CaCl(2) solutions. The presence of dissolved background humic acid and alginate in solutions both significantly retarded EPS deposition on silica surfaces due to the greater steric and electrostatics repulsion.     

Adsorption of simple fluid on silica surface and nanopore: effect of surface chemistry and pore shape

This paper reports a molecular simulation study on the adsorption of simple fluids (argon at 77 K) on hydroxylated silica surfaces and nanopores. The effect of surface chemistry is addressed by considering substrates with either partially or fully hydroxylated surfaces. We also investigate the effect of pore shape on adsorption and capillary condensation by comparing the results for cylindrical and hexagonal nanopores having equivalent sections (i.e., equal section areas). Due to the increase in the polarity of the surface with the density of OH groups, the adsorbed amounts for fully hydroxylated surfaces are found to be larger than those for partially hydroxylated surfaces. Both the adsorption isotherms for the cylindrical and hexagonal pores conform to the typical behavior observed in the experiments for adsorption/condensation in cylindrical nanopores MCM-41. Capillary condensation occurs through an irreversible discontinuous transition between the partially filled and the completely filled configurations, while evaporation occurs through the displacement at equilibrium of a hemispherical meniscus along the pore axis. Our data are also used to discuss the effect of surface chemistry and pore shape on the BET method. The BET surface for fully hydroxylated surfaces is much larger (by 10-20%) than the true geometrical surface. In contrast, the BET surface significantly underestimates the true surface when partially hydroxylated surfaces are considered. These results suggest that the surface chemistry and the choice of the system adsorbate/adsorbent is crucial in determining the surface area of solids using the BET method.     

Organically modified silica: synthesis and applications due to its surface interaction with organic molecules

Silica gels can be chemically modified using organic precursors producing organically modified silica (ORMOSIL), a class of novel materials for hosting varieties of organic and inorganic substrates. Ormosil matrixed materials show an enhanced activity during catalysis, photochemical activities like absorption and emission, electrochemical sensitivities, sensing of gases, solvents, pH of solution and biomolecules, etc. Ormosil-based materials can be used as efficient protective coatings and can be utilized in designing wave guides that can carry out excellent photonic transmission of information. The synthetic and chemical modification of ormosil and some of the above applications have been discussed.     

Dynamic characteristics of molecules,grafted to a silica surface

The mobility of nitroxyl radicals, grafted to silica, depends essentially on the method of attachment to the surface, the composition of the medium, and the temperature. The presence in the grafted molecules of functional groups, interacting with the silanol groups, reduces significantly the mobility of the attached molecules. The transition from hydrocarbons to polar solvents noticeably increases the mobility of the grafted groups.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 6, pp. 701–707, November–December, 1988.     

Adsorption and preconcentration of 2,4-dichlorophenoxyacetic acid on a chemically modified silica gel surface

The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D), chemically anchored to a silica gel surface, was used to adsorb and preconcentrate the same herbicide from aqueous solutions at room temperature. From a series of adsorption isotherms adjusted to a modified Langmuir equation, the maximum number of moles adsorbed was calculated as 4.67 x 10(-5) mol g(-1), with the highest retention capacity at pH 5. This modified silica gel was used in a column for preconcentrating trace levels of 2,4-D. The preconcentrated herbicide can be directly eluted with methanol with a recovery efficiency higher than 97%. The concentration factor was 8.33.     

Adsorption of a cationic surfactant, miramistin, from aqueous solutions on the surface of highly dispersed silica

The adsorption of a universal antiseptic agent, the cationic surfactant miramistin, on the surface of highly dispersed silica has been studied. It has been shown that, when miramistin is adsorbed from acidic premicellar solutions, the main contribution to miramistin binding with the surface is made by hydrogen bonding between amide groups of surfactant molecules and silanol groups of silica, which is, at higher pH values, accompanied by ionic interaction between positively charged quaternary nitrogen atoms of miramistin and negatively charged dissociated silanol groups. In the case of adsorption from a micellar solution, an increase in the surface concentration of miramistin is almost independent of solution pH, because the second layer is predominantly formed due to hydrophobic interactions.     

Adsorption and desorption behaviors of DNA with magnetic mesoporous silica nanoparticles

The interaction between DNA and mesopores is one of the basic concerns when mesoporous silica nanoparticle (MSN) is used as a DNA carrier. In this work, we have synthesized a type of mesoporous silica nanoparticle that has a Fe(3)O(4) inner core and mesoporous silica shell. This magnetic mesoporous silica nanoparticle (denoted as M-MSN) offers us a convenient platform to manipulate the DNA adsorption and desorption processes as it can be easily separated from solution by applying a magnetic field. The DNA adsorption behavior is studied as a function of time in chaotropic salt solution. The maximum amount of adsorbed DNA is determined as high as 121.6 mg/g. We have also developed a method to separate the DNA adsorbed onto the external surface and into the mesopores by simply changing temperature windows. The desorption results suggest that, within the whole adsorbed DNA molecules, about 89.5% has been taken up by M-MSN mesopores. Through the dynamic light scattering experiment, we have found that the hydrodynamic size for M-MSN with DNA in its mesopores is higher than the naked M-MSN. Finally, the preliminary result of the adsorption mechanism study suggests that the DNA adsorption into mesopores may generate more intermolecular hydrogen bonds than those formed on the external surface.