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The lipopeptide surfactin produced by certain strains of Bacillus subtilis is a powerful biosurfactant possessing potentially useful antimicrobial properties. In order to better understand its surface behavior, we have used surface sensitive sum frequency generation (SFG) vibrational spectroscopy in the C—H and C═O stretching regions to determine its structure at the air/water interface. Using surfactin with the leucine groups of the peptide ring perdeuterated, we have shown that a majority of the SFG signals arise from the 4 leucine residues. We find that surfactin forms a robust film, and that its structure is not affected by the number density at the interface or by pH variation of the subphase. The spectra show that the ring of the molecule lies in the plane of the surface rather than perpendicular to it, with the tail lying above this, also in the plane of the interface.

In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be applied to a large number of molecules thanks to the technical development of lasers and detectors over the last decades, and is a complementary and visual alternative to traditional MS to be used in environments difficult to asses with MS. In this article we will review general considerations when performing PLIF experiments, our experimental set-up for PLIF and discuss relevant examples of PLIF applied to catalysis.

Number of trace compounds (called biomarkers), which occur in human breath, provide an information about individual feature of the body, as well as on the state of its health. In this paper we present the results of experiments about detection of certain biomarkers using laser absorption spectroscopy methods of high sensitivity. For NO, OCS, C₂H₆, NH₃, CH₄, CO and CO(CH₃)₂ an analysis of the absorption spectra was performed. The influence of interferents contained in exhaled air was considered. Optimal wavelengths of the detection were found and the solutions of the sensors, as well as the obtained results were presented. For majority of the compounds mentioned above the detection limits applicable for medicine were achieved. The experiments showed that the selected optoelectronic techniques can be applied for screening devices providing early diseases detection.

Broadband, mid-infrared supercontinuum generation in a step-index fluoroindate fibre is reported. By using ~70-picosecond laser pulses at 2.02 μm, provided by an optical parametric generator, a wide spectrum with a cut-off wavelength at 5.25 μm and a 5-dB bandwidth covering the entire 2–5 μm spectral interval has been demonstrated for the first time. The behaviour of the supercontinuum was investigated by changing the peak power and the wavelength of the pump pulses. This allowed the optimal pumping conditions to be determined for the nonlinear medium that was used. The optical damage threshold for the fluoroindate fibre was experimentally found to be ~200 GW/cm².

Sum-frequency generation vibrational spectroscopy (SFG-VS) can provide detailed information and understanding of the molecular composition, interactions, and orientational and conformational structure of surfaces and interfaces through quantitative measurement and analysis. In this review, we present the current status of and discuss important recent developments in the measurement of intrinsic SFG spectral lineshapes and formulations for polarization measurements and orientational analysis of SFG-VS spectra. The focus of this review is to present a coherent description of SFG-VS and discuss the main concepts and issues that can help advance this technique as a quantitative analytical research tool for revealing the chemistry and physics of complex molecular surfaces and interfaces.

Vibrational sum-frequency generation (SFG) spectroscopy has become an established technique for in situ surface analysis. While spectral recording procedures and hardware have been optimized, unique data analysis routines have yet to be established. The SFG intensity is related to probing geometries and properties of the system under investigation such as the absolute square of the second-order susceptibility ⁠|χ⁽²⁾|². A conventional SFG intensity measurement does not grant access to the complex parts of χ⁽²⁾ unless further assumptions have been made. It is therefore difficult, sometimes impossible, to establish a unique fitting solution for SFG intensity spectra. Recently, interferometric phase-sensitive SFG or heterodyne detection methods have been introduced to measure real and imaginary parts of χ⁽²⁾ experimentally. Here, we demonstrate that iterative phase-matching between complex spectra retrieved from maximum entropy method analysis and fitting of intensity SFG spectra (iMEMfit) leads to a unique solution for the complex parts of χ⁽²⁾ and enables quantitative analysis of SFG intensity spectra. A comparison between complex parts retrieved by iMEMfit applied to intensity spectra and phase sensitive experimental data shows excellent agreement between the two methods.

The lack of understanding of the temporal effects and the restricted ability to control experimental conditions in order to obtain intrinsic spectral lineshapes in surface sum-frequency generation vibrational spectroscopy (SFG-VS) have limited its applications in surface and interfacial studies. The emergence of high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS) with sub-wavenumber resolution [Velarde et al., J. Chem. Phys., 2011, 135, 241102] offers new opportunities for obtaining and understanding the spectral lineshapes and temporal effects in SFG-VS. Particularly, the high accuracy of the HR-BB-SFG-VS experimental lineshape provides detailed information on the complex coherent vibrational dynamics through direct spectral measurements. Here we present a unified formalism for the theoretical and experimental routes for obtaining an accurate lineshape of the SFG response. Then, we present a detailed analysis of a cholesterol monolayer at the air/water interface with higher and lower resolution SFG spectra along with their temporal response. With higher spectral resolution and accurate vibrational spectral lineshapes, it is shown that the parameters of the experimental SFG spectra can be used both to understand and to quantitatively reproduce the temporal effects in lower resolution SFG measurements. This perspective provides not only a unified picture but also a novel experimental approach to measuring and understanding the frequency-domain and time-domain SFG response of a complex molecular interface.

The ability to achieve sub-wavenumber resolution (0.6 cm⁻¹) and a large signal-to-noise ratio in high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS) allows for the detailed SFG spectral lineshapes to be used in the unambiguous determination of fine spectral features. Changes in the structural spectroscopic phase in SFG-VS as a function of beam polarization and experimental geometry proved to be instrumental in the identification of an unexpected 2.78 ± 0.07 cm⁻¹ spectral splitting for the two methyl groups at the vapor/dimethyl sulfoxide (DMSO, (CH₃)₂SO) liquid interface as well as in the determination of their orientational angles.

This paper reviews recent progress in the studies of buried polymer interfaces using sum frequency generation (SFG) vibrational spectroscopy. Both buried solid/liquid and solid/solid interfaces involving polymeric materials are discussed. SFG studies of polymer/water interfaces show that different polymers exhibit varied surface restructuring behavior in water, indicating the importance of probing polymer/water interfaces in situ. SFG has also been applied to the investigation of interfaces between polymers and other liquids. It has been found that molecular interactions at such polymer/liquid interfaces dictate interfacial polymer structures. The molecular structures of silane molecules, which are widely used as adhesion promoters, have been investigated using SFG at buried polymer/silane and polymer/polymer interfaces, providing molecular-level understanding of polymer adhesion promotion. The molecular structures of polymer/solid interfaces have been examined using SFG with several different experimental geometries. These results have provided molecular-level information about polymer friction, adhesion, interfacial chemical reactions, interfacial electronic properties, and the structure of layer-by-layer deposited polymers. Such research has demonstrated that SFG is a powerful tool to probe buried interfaces involving polymeric materials, which are difficult to study by conventional surface sensitive analytical techniques.

The structure and orientation of amphiphilic α-helix and β-strand model peptide films on self-assembled monolayers (SAMs) have been studied with sum frequency generation (SFG) vibrational spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The α-helix peptide is a 14-mer, and the β-strand is a 15-mer of hydrophilic lysine and hydrophobic leucine residues with hydrophobic periodicities of 3.5 and 2, respectively. These periodicities result in the leucine side chains located on one side of the peptides and the lysine side chains on the other side. The SAMs were prepared from the assembly of either carboxylic acid- or methyl-terminated alkyl thiols onto gold surfaces. For SFG studies, the deuterated analog of the methyl SAM was used. SFG vibrational spectra in the C−H region of air-dried peptides films on both SAMs exhibit strong peaks near 2965, 2940, and 2875 cm⁻¹ related to ordered leucine side chains. The orientation of the leucine side chains was determined from the phase of these features relative to the nonresonant gold background. The relative phase for both the α-helix and β-strand peptides showed that the leucine side chains were oriented away from the carboxylic acid SAM surface and oriented toward the methyl SAM surface. Amide I peaks observed near 1656 cm⁻¹ for the α-helix peptide confirm that the secondary structure is preserved on both SAMs. Strong linear dichroism related to the amide π* orbital at 400.8 eV was observed in the nitrogen K-edge NEXAFS spectra for the adsorbed β-strand peptides, suggesting that the peptide backbones are oriented parallel to the SAM surface with the side chains pointing toward or away from the interface. For the α-helix the dichroism of the amide π* is significantly weaker, probably because of the broad distribution of amide bond orientations in the α-helix secondary structure.