Fourier Transform Infrared Reflection Absorption Spectroscopy Research Articles

Probing Active Sites on Pd/Pt Alloy Nanoparticles by CO Adsorption.

We studied the adsorption of CO on Pd/Pt nanoparticles (NPs) with varying compositions using polarization-dependent Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS) and theoretical calculations (DFT). We prepared PtPd alloy NPs via physical vapor codeposition on α-Al2O3(0001) supports. Our morphological and structural characterization by scanning electron microscopy and grazing incidence X-ray diffraction revealed well-defined, epitaxial NPs. We used CO as a probe molecule to identify the particles' surface active sites. Polarization-dependent FT-IRRAS enabled us to distinguish CO adsorption on top and side facets of the NPs. The role of the Pd/Pt alloy ratio on CO adsorption was investigated by comparing the experimental CO stretching band frequency for different alloy arrangements to the results for pure Pd and Pt NPs. Moreover, we studied the influence of hydrogen adsorption on the NP surface composition. We determined the dependence of the IR bands on the local atomic arrangement via DFT calculations, revealing that both bulk alloy composition and neighboring atoms influence the wavenumber of the bands.

On the dissolution kinetics during acid pickling and Zr-based conversion coating of aluminum alloys using element-resolved electrochemistry

The acid pickling of Al-3at.%Mg, Al-3at.%Cu, and aluminum alloy (AA) 7449-T651 in nitro-sulfuro-ferric acid was investigated using element-resolved electrochemistry (AESEC) in terms of their elemental dissolution kinetics. The influence of this acid pickling on the subsequent Zr-based conversion coating process was also demonstrated on these alloys by monitoring the dissolution rates of the alloying elements during conversion and the final elemental depth profiles from calibrated glow discharge-optical emission spectroscopy (GD-OES). The separate influence of fluoride (F−) and nitrate (NO3−) as additives on the dissolution kinetics was also investigated when added to the conversion coating bath solution. F− increased the dissolution rate of Al but no significant effect was seen on Cu, while NO3− enhanced the dissolution rates of both elements. Fourier-transform infrared reflection absorption spectroscopy (FT-IRRAS) data suggested a greater Zr-fluoride presence if the conversion coating was performed on a non-acid-pickled surface.

Surface behaviour of 1-alkyl-3-methylimidazolium ionic liquids at the air-water interface

The ability of 1-alkyl-3-methylimidazolium ionic liquids, [Cnmim][X], to form layers at the air–water interface has been investigated systematically for the first time: five different chain lengths of the cation, n = 12, 14, 16, 18, 20 were studied, combined with three different anions, namely [N(Tf)2]−, [PF6]− and [Cl]−. The results show that only cations with chains longer than n = 16, combined with the [N(Tf)2]− anion form stable monolayers at the air/water interface, allowing measurable surface pressure vs area per molecule (π-A) isotherms immediately after spreading. The films of [C20mim][N(Tf)2] on water have been characterised using Brewster angle microscopy (BAM), Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS), specular X-ray reflectivity (XRR) and grazing incidence X-ray diffraction (GIXD). Additionally, atomistic molecular dynamics simulations were also performed to obtain a molecular level interpretation of the experimental results. The results are compatible with a transition from an expanded monolayer to a trilayer structure, followed by the 3D collapse of the film.

Ultrathin Amorphous Silica Membrane Enhances Proton Transfer across Solid‐to‐Solid Interfaces of Stacked Metal Oxide Nanolayers while Blocking Oxygen

AbstractA large jump of proton transfer rates across solid‐to‐solid interfaces by inserting an ultrathin amorphous silica layer into stacked metal oxide nanolayers is discovered using electrochemical impedance spectroscopy and Fourier‐transform infrared reflection absorption spectroscopy (FT‐IRRAS). The triple stacked nanolayers of Co3O4, SiO2, and TiO2 prepared by atomic layer deposition (ALD) enable a proton flux of 2400 ± 60 s−1 nm−2 (pH 4, room temperature), while a single TiO2 (5 nm) layer exhibits a threefold lower flux of 830 s−1 nm−2. Based on FT‐IRRAS measurements, this remarkable enhancement is proposed to originate from the sandwiched silica layer forming interfacial SiOTi and SiOCo linkages to TiO2 and Co3O4 nanolayers, respectively, with the O bridges providing fast H+ hopping pathways across the solid‐to‐solid interfaces. Together with the complete O2 impermeability of a 2 nm ALD‐grown SiO2 layer, the high flux for proton transport across multi‐stack metal oxide layers opens up the integration of incompatible catalytic environments to form functional nanoscale assemblies such as artificial photosystems for CO2 reduction by H2O.

Comparative Evaluation of the Photostability of Carbamazepine Polymorphs and Cocrystals

Carbamazepine (CBZ), a widely used antiepileptic, is known to be sensitive to light. The aim of this study was to evaluate the photostabilities of three cocrystals of CBZ (CBZ–succinic acid (SUC), CBZ–saccharin (SAC) form I, and CBZ–SAC form II) illuminated with a D65 fluorescent lamp compared with those of the conventional solid forms: CBZ polymorphs (forms I, II, and III). The order of discoloration determined using a colorimetric measurement was almost consistent with that of the degradation rates estimated using Fourier-transform infrared reflection–absorption spectroscopy, and these parameters of CBZ polymorphs increased in the order of form III, form I, and form II. CBZ–SUC and CBZ–SAC form I significantly suppressed the discoloration and degradation of CBZ compared with the raw CBZ, while CBZ–SAC form II facilitated the discoloration and degradation of CBZ. These results were supported by the results from the low-frequency Raman spectroscopy. The molecular mobility estimated using solid-state nuclear magnetic resonance 1H spin–lattice relaxation time strongly correlated with the degradation rate constant, indicating that molecular mobility significantly decreased following the formation of CBZ–SUC and CBZ–SAC form I and resulted in higher photostability. Overall, CBZ–SUC and CBZ–SAC form I are photostable forms and cocrystallization was proven to be an effective approach to improving the photostability of a photolabile drug.

Interaction of Water with Graphene/Ir(111) Studied by Vibrational Spectroscopy.

Water in confinement exhibits altered properties in molecular arrangement, bonding, and interaction with its neighboring environment, as compared to its bulk counterpart. In this work, periodically arranged D2O nano droplets of ∼1 nm size on top of a graphene/iridium moiré superstructure were investigated by Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS) under ultrahigh vacuum conditions at ∼120 K. The IR bands of D2O clusters differ significantly from those observed for bulk D2O amorphous solid water or crystalline ice phases. Blue-shifted symmetric and asymmetric stretching bands with narrower band widths and modified band intensity ratios were observed, pointing to an enhanced internal order and a reduced nearest neighbor distance. Furthermore, two IR bands of "dangling" deuterium atoms were detected originating from threefold coordinated water molecules at the surface of the clusters and at their interface to the graphene layer. The latter arose only with the transition from the water clusters to an amorphous solid water layer. We propose that upon coalescence, opposing local dipoles trigger a hydrogen bond rearrangement at the interface. Our results represent a first step toward an atomistic understanding of water in confinement.

Bulk Defect Dependence of Low-Temperature Partial Oxidation of Methanol and High-Temperature Hydrocarbon Formation on Rutile TiO2 (110)

Titanium dioxide (TiO2) is among the most studied model (photo)catalyst materials. The influence of surface point defects, like oxygen vacancies and particularly bulk defects such as Ti3+ interstitials, is usually underestimated or even ignored. We present a systematic study under well-defined UHV conditions illustrating the importance of such defects for the thermal reaction of methanol at the rutile TiO2 (110) single crystal surface by using temperature-programmed reaction spectroscopy (TPRS) and Fourier-transform infrared reflection–absorption spectroscopy (FT-IRRAS). It will be shown that the population of different reaction pathways, namely, the partial oxidation of methanol to formaldehyde and the deoxygenation forming hydrocarbons, especially methane, depends on the bulk defect density and the presence or absence of oxygen adsorbates. While at elevated temperatures molecular desorption is pronounced for the less defective substrates, for higher reduction grades the high-temperature deoxygenation ch...

Amyloid-β fibrils assembled on ganglioside-enriched membranes contain both parallel β-sheets and turns

Some protein and peptide aggregates, such as those of amyloid-β protein (Aβ), are neurotoxic and have been implicated in several neurodegenerative diseases. Aβ accumulates at nanoclusters enriched in neuronal lipids called gangliosides in the presynaptic neuronal membrane, and the resulting oligomeric and/or fibrous forms accelerate the development of Alzheimer's disease. Although the presence of Aβ deposits at such nanoclusters is known, the mechanism of their assembly and the relationship between Aβ secondary structure and topography are still unclear. Here, we first confirmed by atomic force microscopy that Aβ40 fibrils can be obtained by incubating seed-free Aβ40 monomers with a membrane composed of sphingomyelin, cholesterol, and the ganglioside GM1. Using Fourier transform infrared (FTIR) reflection-absorption spectroscopy, we then found that these lipid-associated fibrils contained parallel β-sheets, whereas self-assembled Aβ40 molecules formed antiparallel β-sheets. We also found that the fibrils obtained at GM1-rich nanoclusters were generated from turn Aβ40 Our findings indicate that Aβ generally self-assembles into antiparallel β-structures but can also form protofibrils with parallel β-sheets by interacting with ganglioside-bound Aβ. We concluded that by promoting the formation of parallel β-sheets, highly ganglioside-enriched nanoclusters help accelerate the elongation of Aβ fibrils. These results advance our understanding of ganglioside-induced Aβ fibril formation in neuronal membranes and may help inform the development of additional therapies for Alzheimer's disease.

Effect of Corrosion Inhibitors on Chromate-free Passivation of Hot-Dip Galvanized Steel

Commercially available passivation methods for white-rust protection of Hot-Dip Galvanized steel have been applied for chromate passivation. However, hexavalent chromium (Cr-VI) is highly toxic and carcinogenic. Therefore, in this paper, we put forth a new means for white-rust protection of Hot-Dip Galvanized steel based on the effects of corrosion inhibitors. In this study, the passivation solution combines the advantages of inorganic salt passivation, silane passivation and resin passivation. The corrosion resistance of the inorganic and organic composite passivation films with corrosion inhibitors was determined by a neutral salt spray test and electrochemical Tafel polarization curves. The surface chemistry of the coatings was monitored by scanning electron microscopy (SEM), X-ray Photoelectron spectroscopy (XPS) and Fourier transform infrared reflection absorption spectroscopy (FTIR). And further studying on the formation mechanism of the passivation film was carried out. The SEM indicated that the top surface of the passivation film was transparent, smooth, uniform and compact. The XPS and FTIR results showed that the passivation film consisted mainly of organic functional groups including-(CH2)n-, -OH, N-H, C=O, C-Si, C-O-C, C-N, Si-O-Si, Si-O-C and so on. The corrosion resistance of passivation film with corrosion inhibitors was significantly improved than that of the passivation film without corrosion inhibitor. After 96h of the corrosion test, the corrosion area was found to be less than 5 %, which indicated that the passivation film greatly improved the corrosion resistance of the hot-dip galvanized sheet, and exhibited a very good protective effect so that can met some industrial applications.DOI: http://dx.doi.org/10.5755/j01.ms.24.3.16330

Preparation of Water-Repellent Monomolecular Films by CF<sub>4</sub> Plasma Treatment on Hydrocarbon Monolayers

Hydrocarbon monomolecular films were prepared on a glass slide with a chemical adsorption technique. Water-repellent fluorocarbon monomolecular films were prepared by CF4 plasma treatment on the chemically adsorbed hydrocarbon monomolecular films. However, the monomolecular films were usually removed by sputtering when the CF4 plasma was treated, because CF4 plasma contains ions of the fluorocarbon fragments, not only its radicals. Therefore, fluorocarbon ions were removed from the plasma by mesh connected to the earth, and then only fluorocarbon radicals were used for treatment in order to prevent the monomolecular film from being removed. Fourier-transform infrared reflection absorption spectroscopy (FTIR-RAS) revealed that the hydrocarbon groups or hydrogens of the hydrocarbon monomolecular film were substituted with fluorocarbon or a fluorocarbon radical. In addition, the water drop contact angle of the film slightly increased by the treatment. It was demonstrated that water-repellent monomolecular films can be prepared by CF4 plasma treatment on hydrocarbon monolayers. Thus, the plasma treatment technique may be useful into preparing the highly durable fluorinated monomolecular films with the cross linkage inter adsorbed molecules in the monolayer films.

Sulfamide chemistry applied to the functionalization of self-assembled monolayers on gold surfaces.

Aniline-terminated self-assembled monolayers (SAMs) on gold surfaces have successfully reacted with ArSO2NHOSO2Ar (Ar = 4-MeC6H4 or 4-FC6H4) resulting in monolayers with sulfamide moieties and different end groups. Moreover, the sulfamide groups on the SAMs can be hydrolyzed showing the partial regeneration of the aniline surface. SAMs were characterized by water contact angle (WCA) measurements, Fourier-transform infrared reflection absorption spectroscopy (IRRAS) and X-ray photoelectron spectroscopy (XPS).

Regio-selective lipase catalyzed hydrolysis of oxanorbornane-based sugar-like amphiphiles at air–water interface: A polarized FT-IRRAS study

Interfacial hydrolysis of oxanorbornane-based amphiphile (Triol C16) by Candida rugosa lipase was investigated using real-time polarized Fourier transform-infrared reflection absorption spectroscopy (FT-IRRAS). The kinetics of hydrolysis was studied by analyzing the ester carbonyl ν(CO) stretching vibration band across the two dimensional (2D) array of molecules at the confined interface. In particular, we demonstrate Triol C16 to form Michaelis-Menten type complex, like that of lipid-substrate analogues, where the Triol C16 head group remained accessible to the catalytic triad of the lipase. The enzyme-induced selective cleavage of the ester bond was spectroscopically monitored by the disappearance of the intense ν(CO) resonance at 1736cm−1. Consequently, the in situ spectroscopic measurements evidenced selective ester hydrolysis of Triol C16 yielding Tetrol C2OH and Palmitic acid, which remained predominantly in the undissociated form at the interface. The conformation sensitive amide I (majorly ν(CO)) and the interfacial water reorganization suggested 2D ordering of the enzyme molecules following which interfacial reactions were employed towards probing the enzyme kinetics at the air/water interface. The investigation demonstrated further the potential of IRRAS spectroscopy for real-time monitoring the hydrolytic product formation and selectivity at biomimetic interfaces.

Spectroscopic Study of Plasma Polymerized a-C:H Films Deposited by a Dielectric Barrier Discharge.

Plasma polymerized a-C:H thin films have been deposited on Si (100) and aluminum coated glass substrates by a dielectric barrier discharge (DBD) operated at medium pressure using C2Hm/Ar (m = 2, 4, 6) gas mixtures. The deposited films were characterized by Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS), Raman spectroscopy, and ellipsometry. FT-IRRAS revealed the presence of sp3 and sp2 C–H stretching and C–H bending vibrations of bonds in the films. The presence of D and G bands was confirmed by Raman spectroscopy. Thin films obtained from C2H4/Ar and C2H6/Ar gas mixtures have ID/IG ratios of 0.45 and 0.3, respectively. The refractive indices were 2.8 and 3.1 for C2H4/Ar and C2H6/Ar films, respectively, at a photon energy of 2 eV.

Surface Acid–Base Properties of Anion-Adsorbed Species at Pt(111) Electrode Surfaces in Contact with CO2-Containing Perchloric Acid Solutions

Carbonate and bicarbonate adsorption on Pt(111) electrodes from CO2-saturated acidic solutions is investigated by cyclic voltammetry and Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS). Spectroscopic results show carbonate and bicarbonate adsorption even at pH = 1, where bulk concentration of these anions is negligible. Moreover, analysis of the potential dependence of band intensities corresponding to adsorbed carbonate and bicarbonate reveals an effect of the electrode potential on the surface acid–base equilibrium. In this regard, increasing potentials favor bicarbonate deprotonation, leading to carbonate formation. A tentative thermodynamic analysis is given to rationalize these trends.

Role of anode material on the electrochemical oxidation of methyl orange

The anodic oxidation of methyl orange (MO, 5-(4-nitrophenylazo)salicylic acid) has been studied by cyclic voltammetry and bulk electrolysis, using a range of electrode materials such as Ti–Ru–Sn ternary oxide, lead dioxide and boron-doped diamond (BDD), glassy carbon (GC) and gold anodes. The results of voltammetries show that with all the electrode materials, in the potential region before oxygen evolution, the oxidation of MO involves simple electrode transfer that produces a polymeric film that deactivates the electrode surface, as confirmed by Fourier Transform Infrared Reflection-Absorption Spectroscopy (FTIRRAS) analysis. A very different behaviour was observed among the electrodes in the region of water decomposition. While BDD and PbO2 regained their initial activity by simple polarisation at 2.3 V vs. saturated calomel electrode (SCE) due to the production of high amount of hydroxyl radicals that destroy the polymeric film, TiRuSnO2, GC and gold cannot be completely reactivated, because they have a low overpotential for oxygen evolution, and this secondary reaction is favoured over polymer mineralization. The results of bulk electrolysis showed that after 3 h of polarisation at 10 mA cm−2, complete colour and chemical oxygen demand (COD) removal were obtained only with BDD anode. Using PbO2 MO was oxidised but a residual COD remains in the solution, while TiRuSnO2 permitted only a partial oxidation of MO.

Deposition and characterization of organic polymer thin films using a dielectric barrier discharge with different C2Hm/N2 (m = 2, 4, 6) gas mixtures

Organic polymer thin films have been deposited on Si(100) and aluminum coated glass substrates by a dielectric barrier discharge (DBD) operated at medium pressure using different C2H m /N2 (m = 2, 4, 6) gas mixtures. The deposited films were characterized by various spectroscopic techniques. Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS) revealed the chemical functional groups present in the films. The surface chemical compositions have been derived from X-ray photo electron spectroscopy (XPS). FT-IRRAS and XPS show the presence of sp, s p 2 and s p 3 bonds of carbon and nitrogen. Various functional groups such as NH containing, saturated and unsaturated alkyl groups have been identified. Thin films obtained from C2H2/N2 and C2H4/N2 gas mixtures revealed a higher N/C ratio when compared to thin films obtained from C2H6/N2. Thickness, refractive index and extinction coefficient were evaluated by spectroscopic ellipsometry (SE). Significant differences between the films obtained with different gas mixtures are observed.

High-precision drop shape analysis (HPDSA) of quasistatic contact angles on silanized silicon wafers with different surface topographies during inclining-plate measurements: Influence of the surface roughness on the contact line dynamics

Contact angles and wetting of solid surfaces are strongly influenced by the physical and chemical properties of the surfaces. These influence quantities are difficult to distinguish from each other if contact angle measurements are performed by measuring only the advancing θa and the receding θr contact angle. In this regard, time-dependent water contact angles are measured on two hydrophobic modified silicon wafers with different physical surface topographies. The first surface is nearly atomically flat while the second surface is patterned (alternating flat and nanoscale rough patterns) which is synthesized by a photolithography and etching procedure. The different surface topographies are characterized with atomic force microscopy (AFM), Fourier transform infrared reflection absorption spectroscopy (FTIRRAS) and Fourier transform infrared attenuated total reflection spectroscopy (FTIR-ATR). The resulting set of contact angle data obtained by the high-precision drop shape analysis approach is further analyzed by a Gompertzian fitting procedure and a statistical counting procedure in dependence on the triple line velocity. The Gompertzian fit is used to analyze overall properties of the surface and dependencies between the motion on the front and the back edge of the droplets. The statistical counting procedure results in the calculation of expectation values E(p) and standard deviations σ(p) for the inclination angle φ, contact angle θ, triple line velocity vel and the covered distance of the triple line dis relative to the first boundary points XB,10. Therefore, sessile drops during the inclination of the sample surface are video recorded and different specific contact angle events in dependence on the acceleration/deceleration of the triple line motion are analyzed. This procedure results in characteristically density distributions in dependence on the surface properties. The used procedures lead to the possibility to investigate influences on contact angles more in detail.

Structure and dynamics of H2O vis-á-vis phenylalanine recognition at a DPPC lipid membrane via interfacial H-bond types: insights from polarized FT-IRRAS and ADMP simulations.

Preferential and enantioselective interactions of L-/D-Phenylalanine (L-Phe and D-Phe) and butoxycarbonyl-protected L-/D-Phenylalanine (LPA and DPA) as guest with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (L-DPPC) as host were tapped by using real time Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS). Polarization-modulated FT-IRRAS of DPPC monolayers above the phenylalanine modified subphases depicted fine structure/conformation differences under considerations of controlled 2D surface pressure. Selective molecular recognition of D-enantiomer over L-enantiomer driven by the DPPC head group via H-bonding and electrostatic interactions was evident spectroscopically. Accordingly, binding constants (K) of 145, 346, 28, and 56 M(-1) for LPA, DPA, L-Phe, and D-Phe, respectively, were estimated. The real time FT-IRRAS water bands were strictly conformation sensitive. The effect of micro-solvation on the structure and stability of the 1:1 diastereomeric L-lipid⋯, LPA/DPA and L-lipid⋯, (L/D)-Phe adducts was investigated with the aid of Atom-centered Density Matrix Propagation (ADMP), a first principle quantum mechanical molecular dynamics approach. The phosphodiester fragment was the primary site of hydration where specific solvent interactions were simulated through single- and triple- "water-phosphate" interactions, as water cluster's "tetrahedral dice" to a "trimeric motif" transformation as a partial de-clusterization was evident. Under all the hydration patterns considered in both static and dynamic descriptions of density functional theory, L-lipid/D-amino acid enantiomer adducts continued to be stable structures while in dynamic systems, water rearranged without getting "squeezed-out" in the process of recognition. In spite of the challenging computational realm of this multiscale problem, the ADMP simulated molecular interactions complying with polarized vibrational spectroscopy unraveled a novel route to chiral recognition and interfacial water structure.

Gradiently varied chain packing/orientation states of polymer thin films revealed by polarization-dependent infrared absorption

Gradiently varied chain packing/orientation states of the polyacrylamide (PAL) thin films spin-coated on the gold (Au) substrates were found via the polarized reflection–absorption Fourier transform infrared spectroscopy (RA-FTIR). As the film thickness increases, the splitted amide I bands provide a direct evidence that the PAL thin films are of a gradiently varied bi-layered structure. In the bottom layer, most of the PAL molecules show random orientation which is induced by the non-favorable interaction from the adjacent Au surface. In the top layer, most of PAL molecules show parallel orientation to the Au surface which is induced by spin coating, evidenced by the enhanced low-frequency splitted amide I band (∼1658cm−1) and N–H stretching modes of the amino groups when the light electric field vector is adjusted to be parallel to the Au surface. The observation reported in this study should be of universal significance for polymer thin films on the supported substrates, where the interfacial interaction as well as spin coating could vary the polymer packing/orientation states substantially.

Tribology and Stability of Organic Monolayers on CrN: A Comparison among Silane, Phosphonate, Alkene, and Alkyne Chemistries

The fabrication of chemically and mechanically stable monolayers on the surfaces of various inorganic hard materials is crucial to the development of biomedical/electronic devices. In this Article, monolayers based on the reactivity of silane, phosphonate, 1-alkene, and 1-alkyne moieties were obtained on the hydroxyl-terminated chromium nitride surface. Their chemical stability and tribology were systematically investigated. The chemical stability of the modified CrN surfaces was tested in aqueous media at 60 °C at pH 3, 7, and 11 and monitored by static water contact angle measurements, X-ray photoelectron spectroscopy (XPS), ellipsometry, and Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS). The tribological properties of the resulting organic monolayers with different end groups (fluorinated or nonfluorinated) were studied using atomic force microscopy (AFM). It was found that the fluorinated monolayers exhibit a dramatic reduction of adhesion and friction force as well as excellent wear resistance compared to those of nonfluorinated coatings and bare CrN substrates. The combination of remarkable chemical stability and superior tribological properties makes these fluorinated monolayers promising candidates for the development of robust high-performance devices.