Spectroscopy | EPFL Graph Search

Spectroscopy is the field of study that measures and interprets the electromagnetic spectra that result from the interaction between electromagnetic radiation and matter as a function of the wavelength or frequency of the radiation. Matter waves and acoustic waves can also be considered forms of radiative energy, and recently gravitational waves have been associated with a spectral signature in the context of the Laser Interferometer Gravitational-Wave Observatory (LIGO). In simpler terms, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum. Historically, spectroscopy originated as the study of the wavelength dependence of the absorption by gas phase matter of visible light dispersed by a prism. Spectroscopy, primarily in the electromagnetic spectrum, is a fundamental exploratory tool in the fields of astronomy, chemistry, materials science, and physics, allowing the compos

A Combination of Cold Ion Spectroscopy and Ion Mobility for the Study of Complex Peptides and Small Proteins

Georgios Papadopoulos

We present in this work experiments that push the limits of cold ion spectroscopy to the study of complex peptides and small proteins in the gas phase. Although the low temperature attainable in a cold ion trap greatly simplifies the electronic spectra of large molecules, conformational heterogeneity can still be a significant source of congestion, complicating spectroscopic analysis. To overcome this hurdle, we propose an in tandem combination of ion mobility spectrometry and photofragment spectroscopy. This permits for conformational separation prior to laser interrogation. Towards this end, we describe a proof-of-principle experiment where we combine high- Field Asymmetric waveform Ion Mobility Spectrometry (FAIMS) with electronic spectroscopy. We demonstrate that using FAIMS to separate gas-phase peptide conformers before injecting them into a cold ion trap allows one to decompose a dense spectrum into contributions from different conformational families. In the inverse sense, cold ion spectroscopy can be used as a conformation-specific detector for ion mobility, allowing one to separate an unresolved mobility peak into contributions from different conformational families. The doubly protonated peptide bradykinin serves as a good test case for the marriage of these two techniques as it exhibits a considerable degree of conformational heterogeneity that results in a highly congested electronic spectrum. Our results demonstrate the feasibility and advantages of directly coupling ion mobility with spectroscopy and provide a diagnostic of conformational isomerization of this peptide after being produced in the gas phase by electrospray. In a second series of studies we show the potential but also the limitations of our spectroscopic approach for investigating small, naturally occurring proteins, by applying it to ubiquitin, a protein of 76 amino acids. We present electronic photofragment spectra of various protonation states of ubiquitin and we compare our results to literature data acquired by ion mobility spectrometry. These experiments show that the information obtained by laser interrogation of molecules of this size is limited and could be enhanced by a combination with ion mobility techniques. Although some of the results obtained may be important in characterizing small proteins in the gas phase, these experiments are at an early stage and the application of photofragment spectroscopy on proteins needs more investigation.

EPFL2012

GHz spectroscopy on a rare-earth quantum magnet

Lev Bergsma

In this report, spectroscopy was used to track the energy of different states in a LiHoF4 sample around its critical temperature. The experimental setup consist of a Cooper cavity with the sample, an antenna and a resonator inside. This cavity is attached to a probe and put inside a cooled well and a transverse magnetic field. Two different frequency ranges were examined around, f0 = (1.18732 0.00001) Ghz and f0 = (3.32940 0.00001) Ghz. The energy difference between states was successfully tracked for different temperatures thanks to the Q factor plots. However, the lack of sufficient data points and the unexpected behaviour around Tc (there are no gaps and no discontinuities), implies that this is only the beginning of this experiment and more time and measurements is needed to claim reasonable results.

2022

Evanescent wave gas sensing based on modulation spectroscopy

Daniel Salzmann

In recent years, optical gas detectors based on a tunable diode laser absorption spectrometer has become more and more important for monitoring trace gases in atmospheric, medical, and industrial processes. In the medical field, blood gases, essentially pO2 and pCO2, are vital parameters for patient respiratory status monitoring. Typically, hypoxaemia or hypercapnia can be very harmful, especially for neonates, and requires continuous monitoring for rapid clinical intervention. Transcutaneous blood gases, permeating through the skin, can be continuously measured in patients by electrochemical sensors applied to the surface of the skin. These sensors suffer specific instability and must be re-calibrated. For this reason, the present thesis explores a new concept of gas sensors, applying light absorption at the surface of an integrated optics waveguide and using the advantages of a modulated spectroscopy technique for sensitivity and selectivity enhancement. In other words, the present thesis sets a mathematical model and demonstrates experimentally a new concept of evanescent wave gas sensing based on modulation spectroscopy. The field of application considered in this book is restricted to gas detection, however the concept can also be applied to the detection of liquids. In particular, we demonstrate the potential applicability of the concept to transcutaneous blood gas monitoring, and especially carbon dioxide monitoring. The system transfer function modelization of the concept includes carbon dioxide absorption spectrum in the near-infrared region (1.6µm), laser diode modulation spectroscopy assuming optical frequency modulation (FM) as well as intensity modulation (IM) induced by current modulation, and integrated optics sensor-head transmission. The modelization evidences that the silicon nitride technology has the advantage of: high evanescent wave sensitivity (8% for the selected TE mode), low propagation loss, possibility of strong curvatures for miniaturization and availability of fiberto- waveguide mode matching technique (taper). In the modelization, we evidence that the optimal waveguide length equals the inverse of the propagation loss which is mainly limited by the waveguide scattering. Also, we demonstrate that the implementation of a fiber-to-waveguide mode matching taper at both waveguide ends, drastically decreases the resonance limitation of the system resolution. Experimentally, the transfer function of the concept is validated and characterized based on a free-space modulation spectroscopy setup whose performance, in terms of second harmonic resolution, is first measured at 3.55 · 10-6 1/√Hz corresponding to 0.275 mmHg/√Hz CO2 partial pressure. In the chosen region of 200-400MHz of frequency modulation, we confirm that the 1/f-noise is negligible and the dominating amplifier noise can be approximated by the thermal noise. In the case of high insertion loss and short interaction length the interferometric noise (or etalon-effect) becomes the system resolution limitation. By the insertion of a prism coupled planar waveguide instead of the free-space cell, we demonstrate the concept of integrated optics evanescent wave sensing based on modulation spectroscopy. The system characterization is completed by the validation of the evanescent wave sensitivity in gas of about 8% for a laterally confined waveguide. The outlook of a transcutaneous blood gas monitoring instrument is also established. We first extrapolate the expected waveguide characteristics to show that a resolution of 1mmHg CO2 partial pressure can be reached in 4.5 to 12sec response-time. Then, the requirement of a maximal sensing area of 10mm diameter is at the origin of two geometries of sensor-head: a crossing spiral and a non-crossing double spiral. We verify experimentally a propagation loss as low as 0.5dB/cm and observe a stringent tolerance for light injection. The latter requires an integrated device for mode matching and pigtailing. After implementation of a taper at both waveguide ends, we demonstrate the drastic reduction of the total coupling loss. The carbon dioxide measurements reveal a relatively deep pattern on the second harmonic signal that tends to prove that polarization and resonances are coupled together most likely at the waveguide level. Applying nitrogen (N2) as reference gas, the pattern compensation results in the carbon dioxide signature measurement in direct detection only. The next generation, now in process, is a patented pigtailed non-crossing double-spiral sensor-head building the first step towards an industrial prototype. The waveguide miniaturization allows an interaction length longer than 21cm on a 3×3mm area. The improvement towards a high resolution system concerns the propagation loss and the coupling loss on the sensor-head, and concerns the polarization control or scrambling on the modulation spectroscopy setup. We finally conclude, following the demonstration on the planar waveguide and the extrapolation of the measured characteristics, that the concept of evanescent wave gas sensing based on modulation spectroscopy, can compensate the lack of sensitivity of an integrated optics sensor-head and can be applied in gas and liquid sensing. Moreover, based on the sensor-head developments and realistic improvements, we also conclude that the perspective of high resolution sensing system, and in particular for carbon dioxide determination, evidences the potential applicability of the concept to transcutaneous blood gas monitoring. This opens a new optical outlook of continuous and non-invasive blood gas monitoring, applied in medicine for patient respiratory status monitoring.

EPFL2003