Sum Frequency Generation Spectrometer Research Articles

Hybrid high spectral resolution broadband mid-infrared SFG spectrometer development and demonstration.

In this work, we present the development of a femtosecond tunable middle infrared (mid-IR) radiation source for the realization of a hybrid concept compact broadband high-resolution sum-frequency generation (SFG) spectroscopy system. For the realization of the new concept, we used a two-channel picosecond fiber laser as a seed for narrowband (∼1.5 cm-1) and broadband ultrafast radiation sources operating at 1 kHz repetition rate. In order to achieve >500 cm-1 bandwidth widely tunable microjoule level pulses in the mid-IR spectral region (2-10 µm), broadband femtosecond source optimization was performed. Numerical simulations with different nonlinear crystals and optical parametric amplification layouts at given fixed initial conditions paved a way to experimentally realize an optimal scheme for a femtosecond mid-IR channel. Fully operating SFG spectrometer setup was assembled and tested. The developed SFG spectrometer demonstrates a unique combination of parameters: excellent spectral resolution (<3 cm-1) similar to a narrowband scanning picosecond spectrometers and fast simultaneous acquisition of broadband spectra up to more than 850 cm-1.

Two-dimensional sum-frequency generation (2D SFG) spectroscopy: summary of principles and its application to amyloid fiber monolayers.

By adding a mid-infrared pulse shaper to a sum-frequency generation (SFG) spectrometer, we have built a 2D SFG spectrometer capable of measuring spectra analogous to 2D IR spectra but with monolayer sensitivity and SFG selection rules. In this paper, we describe the experimental apparatus and provide an introduction to 2D SFG spectroscopy to help the reader interpret 2D SFG spectra. The main aim of this manuscript is to report 2D SFG spectra of the amyloid forming peptide FGAIL. FGAIL is a critical segment of the human islet amyloid polypeptide (hIAPP or amylin) that aggregates in people with type 2 diabetes. FGAIL is catalyzed into amyloid fibers by many types of surfaces. Here, we study the structure of FGAIL upon deposition onto a gold surface covered with a self-assembled monolayer of methyl-4-mercaptobenzoate (MMB) that produces an ester coating. FGAIL deposited on bare gold does not form ordered layers. The measured 2D SFG spectrum is consistent with amyloid fiber formation, exhibiting both the parallel (a+) and perpendicular (a-) symmetry modes associated with amyloid β-sheets. Cross peaks are observed between the ester stretches of the coating and the FGAIL peptides. Simulations are presented for two possible structures of FGAIL amyloid β-sheets that illustrate the sensitivity of the 2D SFG spectra to structure and orientation. These results provide some of the first molecular insights into surface catalyzed amyloid fiber structure.

Sample cells for probing solid/liquid interfaces with broadband sum-frequency-generation spectroscopy

Two sample cells designed specifically for sum-frequency-generation (SFG) measurements at the solid/liquid interface were developed: one thin-layer analysis cell allowing measurement of films on reflective metallic surfaces through a micrometer layer of solution and one spectroelectrochemical cell allowing investigation of processes at the indium tin oxide/solution interface. Both sample cells are described in detail and data illustrating the capabilities of each are shown. To further improve measurements at solid/liquid interfaces, the broadband SFG system was modified to include a reference beam which can be measured simultaneously with the sample signal, permitting background correction of SFG spectra in real time. Sensitivity tests of this system yielded a signal-to-noise ratio of 100 at a surface coverage of 0.2 molecules/nm(2). Details on data analysis routines, pulse shaping methods of the visible beam, as well as the design of a purging chamber and sample stage setup are presented. These descriptions will be useful to those planning to set up a SFG spectrometer or seeking to optimize their own SFG systems for measurements of solid/liquid interfaces.