Vibrational Spectroscopy of Competitive Adsorption at a Liquid/Solid Interface Using IR-Visible Sum-Frequency Generation PDF Download
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Author: J. Miragliotta Publisher: ISBN: Category : Languages : en Pages : 4
Book Description
Optical IR-Visible sum-frequency generation (SFG), a surface vibrational spectroscopy, has been used to study competitive adsorption at a hydroxylated ZrO2 surface in contact with a number of binary solutions. This technique is similar to surface second harmonic generation (SHG) in that it is forbidden (in the dipole approximation) in spatial regions possessing inversion symmetry. Therefore, systems consisting of an interface bound by centrosymmetric media give rise to a nonlinear response which is dominated by that of the interfacial region. In addition to being surface specific, the SFG signal from the liquid/solid interface can be resonantly enhanced when the incident IR laser source used in the generation process is tuned through a vibrational mode in the adsorbed species, provided the mode is both Raman and IR active. This vibrational information allows identification of the adsorbed molecule as well as measurements of surface coverage, molecular orientation, and adsorbate interactions for a number of the two-component liquid systems.
Author: J. Miragliotta Publisher: ISBN: Category : Languages : en Pages : 4
Book Description
Optical IR-Visible sum-frequency generation (SFG), a surface vibrational spectroscopy, has been used to study competitive adsorption at a hydroxylated ZrO2 surface in contact with a number of binary solutions. This technique is similar to surface second harmonic generation (SHG) in that it is forbidden (in the dipole approximation) in spatial regions possessing inversion symmetry. Therefore, systems consisting of an interface bound by centrosymmetric media give rise to a nonlinear response which is dominated by that of the interfacial region. In addition to being surface specific, the SFG signal from the liquid/solid interface can be resonantly enhanced when the incident IR laser source used in the generation process is tuned through a vibrational mode in the adsorbed species, provided the mode is both Raman and IR active. This vibrational information allows identification of the adsorbed molecule as well as measurements of surface coverage, molecular orientation, and adsorbate interactions for a number of the two-component liquid systems.
Author: Publisher: ISBN: Category : Languages : en Pages : 140
Book Description
Sum frequency generation (SFG) vibrational spectroscopy has been used to study the interfacial structure of several polypeptides and amino acids adsorbed to hydrophobic and hydrophilic surfaces under a variety of experimental conditions. Peptide sequence, peptide chain length, peptide hydrophobicity, peptide side-chain type, surface hydrophobicity, and solution ionic strength all affect an adsorbed peptide's interfacial structure. Herein, it is demonstrated that with the choice of simple, model peptides and amino acids, surface specific SFG vibrational spectroscopy can be a powerful tool to elucidate the interfacial structure of these adsorbates. Herein, four experiments are described. In one, a series of isosequential amphiphilic peptides are synthesized and studied when adsorbed to both hydrophobic and hydrophilic surfaces. On hydrophobic surfaces of deuterated polystyrene, it was determined that the hydrophobic part of the peptide is ordered at the solid-liquid interface, while the hydrophilic part of the peptide appears to have a random orientation at this interface. On a hydrophilic surface of silica, it was determined that an ordered peptide was only observed if a peptide had stable secondary structure in solution. In another experiment, the interfacial structure of a model amphiphilic peptide was studied as a function of the ionic strength of the solution, a parameter that could change the peptide's secondary structure in solution. It was determined that on a hydrophobic surface, the peptide's interfacial structure was independent of its structure in solution. This was in contrast to the adsorbed structure on a hydrophilic surface, where the peptide's interfacial structure showed a strong dependence on its solution secondary structure. In a third experiment, the SFG spectra of lysine and proline amino acids on both hydrophobic and hydrophilic surfaces were obtained by using a different experimental geometry that increases the SFG signal. Upon comparison of these spectra to the SFG spectra of interfacial polylysine and polyproline it was determined that the interfacial structure of a peptide is strongly dependent on its chain length. Lastly, SFG spectroscopy has been extended to the Amide I vibrational mode of a peptide (which is sensitive to peptide secondary structure) by building a new optical parametric amplifier based on lithium thioindate. Evidence is presented that suggests that the interfacial secondary structure of a peptide can be perturbed by a surface.
Author: Andrzej Wieckowski Publisher: John Wiley & Sons ISBN: 1118658965 Category : Science Languages : en Pages : 396
Book Description
Reviews the latest theory, techniques, and applications Surface vibrational spectroscopy techniques probe the structure and composition of interfaces at the molecular level. Their versatility, coupled with their non-destructive nature, enables in-situ measurements of operating devices and the monitoring of interface-controlled processes under reactive conditions. Vibrational Spectroscopy at Electrified Interfaces explores new and emerging applications of Raman, infrared, and non-linear optical spectroscopy for the study of charged interfaces. The book draws from hundreds of findings reported in the literature over the past decade. It features an internationally respected team of authors and editors, all experts in the field of vibrational spectroscopy at surfaces and interfaces. Content is divided into three parts: Part One, Nonlinear Vibrational Spectroscopy, explores properties of interfacial water, ions, and biomolecules at charged dielectric, metal oxide, and electronically conductive metal catalyst surfaces. In addition to offering plenty of practical examples, the chapters present the latest measurement and instrumental techniques. Part Two, Raman Spectroscopy, sets forth highly sensitive approaches for the detection of biomolecules at solid-liquid interfaces as well as the use of photon depolarization strategies to elucidate molecular orientation at surfaces. Part Three, IRRAS Spectroscopy (including PM-IRRAS), reports on wide-ranging systems from small fuel molecules at well-defined surfaces to macromolecular complexes that serve as the building blocks for functional interfaces in devices designed for chemical sensing and electric power generation. The Wiley Series on Electrocatalysis and Electrochemistry is dedicated to reviewing important advances in the field, exploring how these advances affect industry. The series defines what we currently know and can do with our knowledge of electrocatalysis and electrochemistry as well as forecasts where we can expect the field to be in the future.
Author: Publisher: ISBN: Category : Languages : en Pages : 142
Book Description
Sum frequency generation (SFG) vibrational spectroscopy was used to investigate the interfacial properties of several amino acids, peptides, and proteins adsorbed at the hydrophilic polystyrene solid-liquid and the hydrophobic silica solid-liquid interfaces. The influence of experimental geometry on the sensitivity and resolution of the SFG vibrational spectroscopy technique was investigated both theoretically and experimentally. SFG was implemented to investigate the adsorption and organization of eight individual amino acids at model hydrophilic and hydrophobic surfaces under physiological conditions. Biointerface studies were conducted using a combination of SFG and quartz crystal microbalance (QCM) comparing the interfacial structure and concentration of two amino acids and their corresponding homopeptides at two model liquid-solid interfaces as a function of their concentration in aqueous solutions. The influence of temperature, concentration, equilibration time, and electrical bias on the extent of adsorption and interfacial structure of biomolecules were explored at the liquid-solid interface via QCM and SFG. QCM was utilized to quantify the biological activity of heparin functionalized surfaces. A novel optical parametric amplifier was developed and utilized in SFG experiments to investigate the secondary structure of an adsorbed model peptide at the solid-liquid interface.
Author: George J. Holinga Publisher: ISBN: Category : Languages : en Pages : 284
Book Description
Sum frequency generation (SFG) vibrational spectroscopy was used to investigate the interfacial properties of several amino acids, peptides, and proteins adsorbed at the hydrophilic polystyrene solid-liquid and the hydrophobic silica solid-liquid interfaces. The influence of experimental geometry on the sensitivity and resolution of the SFG vibrational spectroscopy technique was investigated both theoretically and experimentally. SFG was implemented to investigate the adsorption and organization of eight individual amino acids at model hydrophilic and hydrophobic surfaces under physiological conditions. Biointerface studies were conducted using a combination of SFG and quartz crystal microbalance (QCM) comparing the interfacial structure and concentration of two amino acids and their corresponding homopeptides at two model liquid-solid interfaces as a function of their concentration in aqueous solutions. The influence of temperature, concentration, equilibration time, and electrical bias on the extent of adsorption and interfacial structure of biomolecules were explored at the liquid-solid interface via QCM and SFG. QCM was utilized to quantify the biological activity of heparin functionalized surfaces. A novel optical parametric amplifier was developed and utilized in SFG experiments to investigate the secondary structure of an adsorbed model peptide at the solid-liquid interface.
Author: D. C. Phillips Publisher: ISBN: Category : Languages : en Pages :
Book Description
Sum frequency generation (SFG) vibrational spectroscopy, atomic force microscopy (AFM), and quartz crystal microbalance (QCM) have been used to study the molecular surface structure, surface topography and mechanical properties, and quantitative adsorbed amount of biological molecules at the solid-liquid interface. The molecular-level behavior of designed peptides adsorbed on hydrophobic polystyrene and hydrophilic silica substrates has been examined as a model of protein adsorption on polymeric biomaterial surfaces. Proteins are such large and complex molecules that it is difficult to identify the features in their structure that lead to adsorption and interaction with solid surfaces. Designed peptides which possess secondary structure provide simple model systems for understanding protein adsorption. Depending on the amino acid sequence of a peptide, different secondary structures ({alpha}-helix and {beta}-sheet) can be induced at apolar (air/liquid or air/solid) interfaces. Having a well-defined secondary structure allows experiments to be carried out under controlled conditions, where it is possible to investigate the affects of peptide amino acid sequence and chain length, concentration, buffering effects, etc. on adsorbed peptide structure. The experiments presented in this dissertation demonstrate that SFG vibrational spectroscopy can be used to directly probe the interaction of adsorbing biomolecules with a surface or interface. The use of well designed model systems aided in isolation of the SFG signal of the adsorbing species, and showed that surface functional groups of the substrate are sensitive to surface adsorbates. The complementary techniques of AFM and QCM allowed for deconvolution of the effects of surface topography and coverage from the observed SFG spectra. Initial studies of biologically relevant surfaces are also presented: SFG spectroscopy was used to study the surface composition of common soil bacteria for use in bioremediation of nuclear waste.
Author: Publisher: John Wiley & Sons ISBN: 3527616918 Category : Science Languages : en Pages : 445
Book Description
This ninth volume in the series concentrates on in situ spectroscopic methods and combines a balanced mixture of theory and applications, making it highly readable for chemists and physicists, as well as for materials scientists and engineers. As with the previous volumes, all the chapters continue the high standards of this series, containing numerous references to further reading and the original literature, for easy access to this new field. The editors have succeeded in selecting highly topical areas of research and in presenting authors who are leaders in their fields, covering such diverse topics as diffraction studies of the electrode-solution interface, thin organic films at electrode surfaces, linear and non-linear spectroscopy as well as sum frequency generation studies of the electrified solid-solution interface, plus quantitative SNIFTIRS and PM-IRRAS. Special attention is paid to recent advances and developments, which are critically and thoroughly discussed. The result is a compelling set of reviews, serving equally well as an excellent and up-to-date source of information for experienced researchers in the field, as well as as an introduction for newcomers.
Author: J. Miragliotta
Author: J. Miragliotta
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Author: Zheng Yang
Author: Andrzej Wieckowski
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Author: George J. Holinga
Author: D. C. Phillips
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Author: Luning Zhang
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