Surface-enhanced vibrational investigation of adsorbed analgesics

Adsorption properties of acetylsalicylic acid (AA), ibuprofen and acetaminophen deposited from volatile solvents with varying protic/aprotic properties on vacuum-evaporated silver films were characterized using surface-enhanced infrared absorption (SEIRA) and surface-enhanced Raman spectroscopy (SERS). SERS preferentially enhances monolayer Raman shifts, while SEIRA can enhance the infrared absorbance of the monolayer and multilayers. To our best knowledge, this is the first reported study of these molecules using a combination of SERS/SEIRA. SERS revealed that AA and ibuprofen adsorbed ionically in monolayers, independent of the deposition solvents used in the process. SEIRA experiments showed that AA multilayers condensed molecularly using a deposition solvent with polar bonds. However, when an alkane deposition solvent with non-polar bonds such as n-heptane was used, AA adsorbed as acetylsalicylate ions in the first few multilayers, while ibuprofen always adsorbed as the free acid in the multilayer. These ionization trends depend upon the affinity of AA and ibuprofen for the underlying silver film. TPD experiments on silver powders further demonstrated that ibuprofen affinity for silver was less than AA. Furthermore, SEIRA indicated that acetaminophen adsorbed as multilayers of metastable polymorphs using protic or polar aprotic deposition solvents. Protic deposition solvents gave higher quality SERS spectra of an acetaminophen monolayer in comparison to polar aprotic deposition solvents. Such studies could find significant applications in biochemical and nanotechnology processes such as drug delivery, catalysis, and tissue engineering and will contribute to the understanding of the impact and fate of analgesics released into the environment.     

Characterization of aminophenol isomer adsorption on silver nanostructures

Surface-enhanced infrared absorption (SEIRA), temperature-programmed desorption, and density functional theory calculations were used to explore the adsorption of aminophenol isomers on vacuum deposited silver films and silver powder. Salts of the aminophenolate ions were synthesized to aid in vibrational spectral interpretation. No evidence for dissociation of any of the aminophenols into aminophenolate ions in the monolayer or multilayer was found when adsorbed on silver nanostructures (SNS). SEIRA demonstrated additional hydrogen-bonding interactions in a multilayer of 2-aminophenol and 3-aminophenol adsorbed on SNS beyond what is present in the aminophenol powders. Surface-enhanced Raman spectroscopy (SERS) experiments also showed that a 2-aminophenol monolayer adsorbed on SNS is photolytically oxidized to either 3-aminophenoxazone or 2,2′-dihydroxyazobenzene, while neither 3-aminophenol nor 4-aminophenol showed any SERS activity. This work is expected to have a significant impact in a range of environmental, biochemical, and industrial applications where phenol chemistry is important.     

Surface-enhanced vibrational spectroscopy of B vitamins: what is the effect of SERS-active metals used?

Surface-enhanced Raman scattering (SERS) spectroscopy and surface-enhanced infrared absorption (SEIRA) spectroscopy are analytical tools suitable for the detection of small amounts of various analytes adsorbed on metal surfaces. During recent years, these two spectroscopic methods have become increasingly important in the investigation of adsorption of biomolecules and pharmaceuticals on nanostructured metal surfaces. In this work, the adsorption of B-group vitamins pyridoxine, nicotinic acid, folic acid and riboflavin at electrochemically prepared gold and silver substrates was investigated using Fourier transform SERS spectroscopy at an excitation wavelength of 1,064 nm. Gold and silver substrates were prepared by cathodic reduction on massive platinum targets. In the case of gold substrates, oxidation–reduction cycles were applied to increase the enhancement factor of the gold surface. The SERS spectra of riboflavin, nicotinic acid, folic acid and pyridoxine adsorbed on silver substrates differ significantly from SERS spectra of these B-group vitamins adsorbed on gold substrates. The analysis of near-infrared-excited SERS spectra reveals that each of B-group vitamin investigated interacts with the gold surface via a different mechanism of adsorption to that with the silver surface. In the case of riboflavin adsorbed on silver substrate, the interpretation of surface-enhanced infrared absorption (SEIRA) spectra was also helpful in investigation of the adsorption mechanism.     

Surface-enhanced Raman scattering interaction of p-aminobenzoic acid on a silver-coated alumina substrate

The adsorption behavior of p-aminobenzoic acid (PABA) molecules on a silver-coated alumina surface-enhanced Raman scattering (SERS) substrate was investigated. For spotted PABA and PABA in non-polar solvents, the PABA molecule is adsorbed flat on the surface of the SERS substrate. In this orientation, the benzene ring is π-bonded to the substrate, and the molecule is further anchored to the substrate by the binding of the lone pairs of NH₂ and COO⁻ groups onto the metal surface. On the other hand, the adsorption behavior of PABA in a polar solvent is greatly influenced by the hydrogen bonding of the amine group with the polar solvent. In this orientation, the molecule is preferentially adsorbed through the COO^± and assumes a non-flat orientation on the metal surface.     

Preparation of a new hydrophilic copolymer from poly(α-hydroxyacrylic acid)

A new hydrophilic copolymer containing α-hydroxy allyl alcohol segments was prepared by reducing poly(α-hydroxyacrylic acid) (PHA) with NaBH₄ in water and mixed solvents of methanol and polar solvents. Conversion to the desired allyl alcohol group in the resultant polymers was confirmed with ICP, FT-IR, and ¹³C NMR spectroscopies. The degree of conversion was as low as 5% for PHA reduced in aqueous solution, while for those reduced in the mixed solvents it was significant (ca. 60–70%).     

Preparation and characterization by surface-enhanced infrared absorption spectroscopy of silver nanoparticles formed on germanium substrates by electroless displacement

In this paper, the feasibility of applying electroless displacement to prepare silver nanoparticles (AgNPs) on the surface of germanium (Ge) substrate is demonstrated, and the performances of surfaces prepared in this manner for surface-enhanced infrared absorption (SEIRA) spectroscopy are reported. The process used to produce suitable AgNPs for SEIRA by electroless deposition is simple and effective, requiring only pretreatment of the germanium surface with hot air, immersion of the substrate in a dilute solution of silver nitrate, and washing of the resulting plate. To quantify the behavior of AgNPs on a Ge substrate and to optimize the conditions for the preparation of AgNPs on Ge substrates, a monolayer of p-nitrothiophenol (PNTP) was bonded to the surface of the AgNPs by immersion of the plate in a dilute solution of PNTP and measurement of the transmission spectrum. The factors that influenced the formation of AgNPs, and hence the SEIRA signals, included the concentration of AgNO₃, the reaction time and the temperature. Results indicated that stronger absorption bands in the SEIRA spectrum of a monolayer of PNTP were obtained if the reaction rate for the displacement of silver ions by Ge was slow. This condition was achieved by keeping the concentration of AgNO₃ and the reaction temperature low. Under the optimal conditions found in this work, an enhancement factor of approximately 100 was achieved for commonly used probe molecules in SEIRA measurements.     

TPD and FT-IRAS investigation of ethylene oxide (EtO) adsorption on a Au(211) stepped surface

Adsorption of ethylene oxide, CH(2)CH(2)O (EtO), on a Au(211) stepped surface was studied by temperature programmed desorption (TPD) and Fourier transform infrared reflection-absorption spectroscopy (FT-IRAS). Ethylene oxide was completely reversibly adsorbed, and desorbed molecularly during TPD following adsorption on Au(211) at 85 K. EtO TPD peaks appeared at 115 K from the multilayer film and 140 and 170 K from the monolayer. Desorption at 140 K was attributed to EtO desorption from terrace sites, and that at 170 K to EtO desorption from step sites. Desorption activation energies and corresponding adsorption energies were estimated to be 8.4 and 10.3 kcal mol(-1), respectively. The EtO ring (C(2)O) deformation band appeared in IRAS at 865 cm(-1) for EtO in multilayer films and when adsorbed in the monolayer at terrace sites. The stronger chemisorption bonding of EtO at Au step sites slightly weakens the bonding within the molecule and causes a small red-shift of this band to 850 cm(-1) for adsorption at step sites. EtO presumably binds via the oxygen atom to the surface, and observation of the EtO-ring absorption band in IRAS establishes that the molecular ring plane of EtO adsorbed at step and terrace sites is nearly upright with respect to the crystal surface plane.     

A unified theory of adsorption and wetting using the percus yevick equation for hard spheres with surface adhesion

Abstract

The recent analysis by Baxter of the Percus-Yevick model for an assembly of similar spherical particles with hard sphere repulsion plus a delta function attraction is generalised to an arbitrary number of components. We use the solution to study one component gas adsorption onto a planar substrate. The resulting adsorption isotherms exhibit monolayer or multilayer wetting according to the strengths of the interaction parameters. In particular, we find that multilayer wetting will not occur if the adsorbate/adsorbate interaction is sufficiently weak regardless of the strength of the adsorbate/adsorbent interaction. For weak adsorbate/ adsorbate interactions at low gas pressures the adsorption saturates at approximately a monolayer as the adsorbate/adsorbent interaction is increased.     

The surface chelate effect

The presence of a surface chelate effect is established in the model system of Cu2+ adsorption on a self-assembled monolayer of 16-mercaptohexadecanoic acid (MHA) on Au. The formation constant of Cu2+ with the MHA surface was found to be 119 +/- 3.2 times greater than that of Cu2+ with succinic acid (HOOC-(CH2)2-COOH), and 213 +/- 4.0 times greater than that of Cu2+ with glutaric acid (HOOC-(CH2)3-COOH) in aqueous solutions. Both of these molecules are known to chelate to metal ions forming seven- and eight-membered rings. The greater surface chelate effect is attributed to the presence of the two-dimensional array of ligands on the surface. We believe the surface chelate effect demonstrated here is of general significance to adsorption on molecular surfaces and should depend strongly on chemical functionality and monolayer structure.     

Adsorption energies, inter-adsorbate interactions, and the two binding sites within monolayer benzene on Ag(111)

The adsorption of monolayer and multilayer benzene on the Ag(111) surface was characterized using temperature programmed desorption (TPD). TPD spectra revealed two broad peaks at approximately 205 and approximately 150 K at submonolayer coverage and a sharper, multilayer peak at 140 K. Analysis of the coverage-dependent shape and shift of the two submonolayer peaks has resulted in their assignment to desorption from two different binding geometries on threefold-hollow sites with symmetries C(3v)(sigma d) and C(3v)(sigma v). The TPD peak analysis incorporated inter-adsorbate repulsive interaction that resulted from the local dipole moment at the adsorption site induced by the adsorbate-surface charge transfer bonding. The analysis has yielded desorption energies of 54.9 +/- 0.8 and 50.4 +/- 0.4 kJ/mol for the C(3v)(sigma d) and C(3v)(sigma v) configurations, respectively. The interface dipole and polarizability of the benzene-silver complex have been determined to be 5.4 +/- 1.8 D and 14 +/- 10 A3, respectively. Repulsive interactions in the monolayer were found to lower the desorption energy from the zero-coverage value by 14.8 kJ/mol. Leading edge analysis of the multilayer peak yielded a desorption energy of 40.9 +/- 0.7 kJ/mol.     

Self-assembly of homopolymer and copolymers of N-4-hydroxyphenyl-acrylamide with diazoresin via H-bonding attraction

A kind of photoactive multilayer utrathin films has been fabricated via H-bonding attraction from hydroxyphenyl containing polymers as H-donor and diazoresin (DR) as H-acceptor by means of a self-assembly technique. The layer-by-layer deposition of two components is monitored spectrometrically and shows that the UV-VIS absorbance of the film increases linearly both at 250 nm (absorption of benzene nucleus) and at 383 nm (absorption of diazonium group), which indicates that the fabrication proceeds regularly. The nature of H-bonding between layers was verified by the determination of IR spectra of the film fabricated directly on a CaF₂ wafer. The stability of the films toward polar solvents increases dramatically after UV irradiation of the films. It was confirmed provisionally that the bond nature between the layers of the film changes from H-bonding to covalent bonding under UV irradiation. The photodecomposition of the -N₂⁺ groups of the film under UV light follows first order reaction kinetics and a mechanism of the photoreaction has been tentatively proposed.     

Polyelectrolyte complex layers: a promising concept for anti-fouling coatings verified by in-situ ATR-FTIR spectroscopy

In-situ attenuated total reflection (ATR)-FTIR spectroscopy enabled studies on the interaction between the differently charged model proteins human serum albumin, lysozyme, immunoglobulin G and multilayer assemblies, which were deposited by alternating adsorption of poly(ethyleneimine) and poly(acrylic acid) onto Si crystals. Low adsorbed protein amounts were observed if the top polyelectrolyte layer and the protein were equally charged, whereas enhanced protein adsorption occurred for electrostatic attraction between protein and top polyelectrolyte layer.     

Activated Carbon Adsorption of Some Phenolic Compounds Present in Agroindustrial Wastewater

Single solute and simultaneous experimental adsorption isotherms of three phenolic compounds: gallic acid, p-hydroxybenzoic acid and syringic acid, have been investigated at 20, 30 and 40°C, using a bituminous coal based activated carbon. Regardless of temperature, the capacity of the activated carbon used to adsorb these compounds presented the following order: syringic acid > p-hydroxybenzoic acid > gallic acid. The increase of temperature slightly favored the adsorption capacity of the phenolic compounds. In binary and ternary component adsorption, experimental data suggest that interactions between adsorbates improve the adsorption capacity of some of the phenolic acid compounds. On the contrary, at high organic concentrations, adsorbed gallic acid was partially removed from the activated carbon surface because of the presence of the other components.     

The adsorption and desorption of ethanol ices from a model grain surface

Reflection absorption infrared spectroscopy (RAIRS) and temperature programed desorption (TPD) have been used to probe the adsorption and desorption of ethanol on highly ordered pyrolytic graphite (HOPG) at 98 K. RAIR spectra for ethanol show that it forms physisorbed multilayers on the surface at 98 K. Annealing multilayer ethanol ices (exposures >50 L) beyond 120 K gives rise to a change in morphology before crystallization within the ice occurs. TPD shows that ethanol adsorbs and desorbs molecularly on the HOPG surface and shows four different species in desorption. At low coverage, desorption of monolayer ethanol is observed and is described by first-order kinetics. With increasing coverage, a second TPD peak is observed at a lower temperature, which is assigned to an ethanol bilayer. When the coverage is further increased, a second multilayer, less strongly bound to the underlying ethanol ice film, is observed. This peak dominates the TPD spectra with increasing coverage and is characterized by fractional-order kinetics and a desorption energy of 56.3+/-1.7 kJ mol(-1). At exposures exceeding 50 L, formation of crystalline ethanol is also observed as a high temperature shoulder on the TPD spectrum at 160 K.     

Ag on Pt(111): Changes in Electronic and CO Adsorption Properties upon PtAg/Pt(111) Monolayer Surface Alloy Formation

The electronic and chemical (adsorption) properties of bimetallic Ag/Pt(111) surfaces and their modification upon surface alloy formation, that is, during intermixing of Ag and Pt atoms in the top atomic layer upon annealing, were studied by X‐ray photoelectron spectroscopy (XPS) and, using CO as probe molecule, by temperature‐programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRRAS), respectively. The surface alloys are prepared by deposition of sub‐monolayer Ag amounts on a Pt(111) surface at room temperature, leading to extended Ag monolayer islands on the substrate, and subsequent annealing of these surfaces. Surface alloy formation starts at ≈600–650 K, which is evidenced by core‐level shifts (CLSs) of the Ag(3d_5/2) signal. A distinct change of the CO adsorption properties is observed when going to the intermixed PtAg surface alloys. Most prominently, we find the growth of a new desorption feature at higher temperature (≈550 K) in the TPD spectra upon surface alloy formation. This goes along with a shift of the CO_ad‐related IR bands to lower wave number. Surface alloy formation is almost completed after heating to 700 K.     

The adsorption of polyoxyethylated nonylphenol in cyclohexane solution

Summary The adsorption of polyoxyethylated nonylphenol on calcium carbonate and on carbon black in cyclohexane was studied and compared with that in water. The adsorption of this nonionic surfactant in cyclohexane on calcium carbonate showed a monolayer adsorption isotherm and that on carbon black showed a multilayer adsorption isotherm. The adsorption cross sectional area,A, of the surfactant molecule increased with the number of the ethylene oxide units,n, in both cases, and expressed by the equationsA=49.1n ^0.34 for the former case andA=270.n ^0.29 for the later case.When either one of the adsorbent or the solvent is polar and the other is nonpolar, the adsorbed molecules form simple oriented monolayer. When both of the adsorbent and the solvent are polar or nonpolar, however, the adsorption takes place in a complicated form and is delicately affected by the impurity and the balance of the polarity of the surfactant molecule.

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Zusammenfassung Die Adsorption von Polyoxyäthylen-nonylphenol an Calciumcarbonat und Ruß in Zyklohexan wurde untersucht und das Adsorptionsverhalten mit den Ergebnissen von wäßrigen Lösungen verglichen, die im letzten Bericht mitgeteilt sind. Die Adsorption dieser nichtionischen oberflächenaktiven Substanz in Zyklohexan an Calciumcarbonat zeigte eine monomolekulare und an Ruß eine höhermolekulare Adsorptionsisotherme. In beiden Fällen nahm der Adsorptionsquerschnitt,A, des oberflächenaktiven Moleküls mit der Anzahl der Äthylenoxid-Einheiten,n, zu, und es galten folgende Werte:A=49.1 n^0.29 im ersten Fall undA=270.n ^0.34 im letzten Fall.Die adsorbierten Moleküle bilden eine einfach orientierte monomolekulare Schicht, wenn von den beiden Komponenten Adsorbens oder Lösungsmittel eines polar und das andere unpolar ist. Wenn jedoch beide polar oder nichtpolar sind, verläuft die Adsorption komplizierter und wird von den Verunreinigungen und der Bilanz der Polarität empfindlich beeinflußt.

     

Reflection absorption infrared spectroscopy and temperature programmed desorption investigations of the interaction of methanol with a graphite surface

Reflection absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD) have been used to investigate the adsorption of methanol (CH(3)OH) on the highly oriented pyrolytic graphite (HOPG) surface. RAIRS shows that CH(3)OH is physisorbed at all exposures and that crystalline CH(3)OH can be formed, provided that the surface temperature and coverage are high enough. It is not possible to distinguish CH(3)OH that is closely associated with the HOPG surface from CH(3)OH adsorbed in multilayers using RAIRS. In contrast, TPD data show three peaks for the desorption of CH(3)OH. Initial adsorption leads to the observation of a peak assigned to the desorption of a monolayer. Subsequent adsorption leads to the formation of multilayers on the surface and two TPD peaks are observed which can be assigned to the desorption of multilayer CH(3)OH. The first of these shows a fractional order desorption, assigned to the presence of hydrogen bonding in the overlayer. The higher temperature multilayer desorption peak is only observed following very high exposures of CH(3)OH to the surface and can be assigned to the desorption of crystalline CH(3)OH.     

Selective Interaction Between Proteins and the Outermost Surface of Polyelectrolyte Multilayers: Influence of the Polyanion Type,pH and Salt

Protein adsorption was studied by in-situ ATR-FT-IR spectroscopy of consecutively deposited polyelectrolyte multilayer systems terminated either with poly(ethyleneimine) (PEI) or polyanions, such as poly-(acrylic acid) (PAC), poly(maleic acid-co-propylene) (PMA-P) or poly(vinyl sulfate) (PVS). The influence of the polyanion type, pH and ionic strength was investigated. Negatively charged human serum albumin (HSA) was strongly repelled by multilayers terminated with weak polyanions (PAC, PMA-P), whereas moderate attraction was observed for those terminated with the strong polyanion PVS. Changing the pH from 7.4 to 5 resulted in enhanced HSA adsorption onto PAC-terminated multilayers. An increase in ionic strength diminished the attractive HSA adsorption onto PEI-terminated multilayers. For the PEI/PAC system, the biomedically relevant adsorption of human fibrinogen (FGN) is determined via its isoelectric point in accordance with three other proteins.     

Fabrication of a Stable Layer‐by‐Layer Thin Film Based on Diazoresin and Phenolic Hydroxy‐Containing Polymers via H‐Bonding

Using the self assembly technique, a stable multilayer films was successfully fabricated from diazoresin (DR) and poly(styrene‐co‐(N‐(p‐hydroxyphenyl)maleimide)) (P(S‐co‐HPMI)) followed by UV irradiation. The driving force of the self‐assembly was confirmed to be H‐bonding attraction between the diazonium group (—N₂⁺) of DR and the phenolic hydroxy group (—Ph—OH) of P(S‐co‐HPMI). A linkage conversion from H‐bond to covalent bond takes place after decomposition of the —N₂⁺ group using UV irradiation. As a result, the stability of the film towards polar solvents increases dramatically.     

Acid/Base Properties and Adsorption of an Azo Dye on Coating Pigments

Adsorption of an anionic disazo dye, Food Black 2 on coating pigments from polar solvents was studied. Pigments (kaolin, precipitated CaCO₃, amorphous SiO₂, TiO₂, Al₂O₃, and talc) were chosen to be representative of those used in paper for ink‐jet printing. The predominating driving force for the adsorption was electrostatic interactions for all the pigments except talc, for which hydrophobic interactions were dominant. Lewis acid‐base properties of the pigments were studied by measuring adsorption of Lewis acid‐probe molecules from both polar and nonpolar media. The pigments studied were found to be amphoteric, containing both acidic and basic surface groups. However, in the presence of polar solvents, the adsorption of acid‐base probe molecules was greatly reduced, which indicates that Lewis acid‐base interactions have only a small influence on the adsorption of azo dyes from polar media such as water.