European Laboratory for Non-Linear Spectroscopy

We review the most recent technological and application advances of quantum cascade lasers, underlining the present milestones and future directions from the Mid-infrared to the Terahertz spectral range. Challenges and developments, which are the subject of the contributions to this focus issue, are also introduced.

In this paper we present calculations on light diffusion with amplification that can explain previous experiments on the spontaneous emission from such a medium. Also we discuss the experimental considerations on realizing a medium that both multiply scatters and amplifies light. In an amplifying random medium different processes can occur. We argue that one can distinguish three regimes depending on the amount of scattering, and discuss these regimes in the context of random laser action. \textcopyright{} 1996 The American Physical Society.

At the 26th AIRAPT conference in 2017, a task group was formed to work on an International Practical Pressure Scale (IPPS). This report summarizes the activities of the task group toward an IPPS ruby gauge. We have selected three different approaches to establishing the relation between pressure (P) and ruby R1-line shift (Δλ) with three groups of optimal reference materials for applying these approaches. Using a polynomial form of the second order, the recommended ruby gauge (referred as Ruby2020) is expressed by: P[GPa]=1.87(±0.01)×103Δλλ01+5.63(±0.03)Δλλ0, where λ0 is the wavelength of the R1-line near 694.25 nm at ambient condition. In June of 2020, the Executive Committee of AIRAPT endorsed the proposed Ruby2020. We encourage high-pressure practitioners to utilize Ruby2020 within its applicable pressure range (up to 150 GPa), so that pressure data can be directly compared across laboratories and amended consistently as better scales emerge in the future.

Experimental work on cold, trapped metastable noble gases is reviewed. The aspects which distinguish work with these atoms from the large body of work on cold, trapped atoms in general is emphasized. These aspects include detection techniques and collision processes unique to metastable atoms. Several experiments exploiting these unique features in fields including atom optics and statistical physics are described. Precision measurements on these atoms including fine structure splittings, isotope shifts, and atomic lifetimes are also discussed.

The effect of periodic and disordered photonic structures on the absorption efficiency of amorphous and crystalline Silicon thin-film solar cells is investigated numerically. We show that disordered patterns possessing a short-range correlation in the position of the holes yield comparable, or even superior, absorption enhancements than periodic (photonic crystal) patterns. This work provides clear evidence that non-deterministic photonic structures represent a viable alternative strategy for photon management in thin-film solar cells, thereby opening the route towards more efficient and potentially cheaper photovoltaic technologies.

The basic features of diamond anvil cells and of the available techniques to study chemical reactions at ultrahigh pressures are reviewed. A number of study cases including reactions of simple molecular systems (like nitrogen, carbon dioxide and monoxide, nitrous oxide), of unsaturated compounds (like acetylene, butadiene, propylene, cyano derivatives) and of aromatics are discussed to illustrate the perspectives of chemical reactivity at ultrahigh pressures.

Action potentials (APs), via the transverse axial tubular system (TATS), synchronously trigger uniform Ca(2+) release throughout the cardiomyocyte. In heart failure (HF), TATS structural remodeling occurs, leading to asynchronous Ca(2+) release across the myocyte and contributing to contractile dysfunction. In cardiomyocytes from failing rat hearts, we previously documented the presence of TATS elements which failed to propagate AP and displayed spontaneous electrical activity; the consequence for Ca(2+) release remained, however, unsolved. Here, we develop an imaging method to simultaneously assess TATS electrical activity and local Ca(2+) release. In HF cardiomyocytes, sites where T-tubules fail to conduct AP show a slower and reduced local Ca(2+) transient compared with regions with electrically coupled elements. It is concluded that TATS electrical remodeling is a major determinant of altered kinetics, amplitude, and homogeneity of Ca(2+) release in HF. Moreover, spontaneous depolarization events occurring in failing T-tubules can trigger local Ca(2+) release, resulting in Ca(2+) sparks. The occurrence of tubule-driven depolarizations and Ca(2+) sparks may contribute to the arrhythmic burden in heart failure.

The frequency of a DFB quantum cascade laser (QCL) emitting at 4.3 microm has been long-term stabilized to the Lamb-dip center of a CO2 ro-vibrational transition by means of first-derivative locking to the saturated absorption signal. Thanks to the non-linear sum-frequency generation (SFG) process with a fiber-amplified Nd:YAG laser, the QCL mid-infrared (IR) radiation has been linked to an optical frequency-comb synthesizer (OFCS) and its absolute frequency counted with a kHz-level precision and an overall uncertainty of 75 kHz.

Dermoscopy is the conventional technique used for the clinical inspection of human skin lesions. However, the identification of diagnostically relevant morphologies can become a complex task. We report on the development of a polarization multispectral dermoscope for the in vivo imaging of skin lesions. Linearly polarized illumination at three distinct spectral regions (470, 530 and 625 nm), is performed by high luminance LEDs. Processing of the acquired images, by means of spectral and polarization filtering, produces new contrast images, each one specific for melanin absorption, hemoglobin absorption, and single scattering. Analysis of such images could facilitate the identification of pathological morphologies.

Abstract The analysis of protein‐based paint media used in paintings is presented using micro‐Raman spectroscopy, carried out with a diode laser emitting at a wavelength of 785 nm. Following a contextualisation of the analysis and ageing of protein‐based binding media, a consideration of the effects of artificial ageing using visible light on the Raman spectra of binding media is given and the interpretation of changes to the Raman spectra of selected binding media is presented. Bands associated with aromatic amino acids are most affected by ageing, but spectra retain diagnostic information for the identification of proteins. Specific changes to the spectra of dairy and collagen‐based binding media are described and explained with reference to the oxidation of amino acids. A multivariate approach using Principal Component Analysis has been chosen for the assessment of the bands in CH stretching region for which a large set of over 150 spectra were recorded from artificially and naturally aged binding media which included egg white, egg yolk, milk and casein, and collagen‐based glues from rabbit skin, ox bone, parchment and sturgeon bladder. Raman spectroscopy has been used for an assessment of the effects of ageing and the detection of degradation due to exposure of light. Multivariate analysis has allowed the differentiation between a large data set of spectra of naturally and artificially aged binding media. Copyright © 2008 John Wiley & Sons, Ltd.

This chapter contains sections titled: Introduction High-Pressure Technical Survey Fundamentals Reactions at Very High Pressure Summary and Conclusions References

In the last few years two-photon microscopy has been used to perform in vivo high spatial resolution imaging of neurons, glial cells and vascular structures in the intact neocortex. Recently, in parallel to its applications in imaging, multi-photon absorption has been used as a tool for the selective disruption of neural processes and blood vessels in living animals. In this review we present some basic features of multi-photon nanosurgery and we illustrate the advantages offered by this novel methodology in neuroscience research. We show how the spatial localization of multi-photon excitation can be exploited to perform selective lesions on cortical neurons in living mice expressing fluorescent proteins. This methodology is applied to disrupt a single neuron without causing any visible collateral damage to the surrounding structures. The spatial precision of this method allows to dissect single processes as well as individual dendritic spines, preserving the structural integrity of the main neuronal arbor. The same approach can be used to breach the blood-brain barrier through a targeted photo-disruption of blood vessels walls. We show how the vascular system can be perturbed through laser ablation leading toward two different models of stroke: intravascular clot and extravasation. Following the temporal evolution of the injured system (either a neuron or a blood vessel) through time lapse in vivo imaging, the physiological response of the target structure and the rearrangement of the surrounding area can be characterized. Multi-photon nanosurgery in live brain represents a useful tool to produce different models of neurodegenerative disease.

The surface of thin-film solar cells can be tailored with photonic nanostructures to allow light trapping in the absorbing medium. This in turn increases the optical thickness of the film and thus enhances their absorption. Such a coherent light trapping is generally accomplished with deterministic photonic architectures. Here, we experimentally explore the use of a different nanostructure, a disordered one, for this purpose. We show that the disorder-induced modes in the film allow improvements in the absorption over a broad range of frequencies and impinging angles.

In this work we present, to our knowledge for the first time, the results of a transient infrared spectroscopic study of the photoinduced valence tautomerism process in cobalt-dioxolene complexes with sub-picosecond time resolution. The molecular systems investigated were [Co(tpa)(diox)]PF(6) (1) and [Co(Me(3)tpa)(diox)]PF(6) (2), where diox = 3,5-di-tert-butyl-1,2-dioxolene; tpa = tris(2-pyridylmethyl)amine and Me(3)tpa its 6-methylated analogue. Complex (1) is present in solution as ls-Co(III)(catecholate) (1-CAT), while (2) as hs-Co(II)(semiquinonate) (2-SQ). DFT calculation of the harmonic frequencies for (1) and (2) allowed us to identify the vibrational markers of catecholate and semiquinonate redox isomers. Irradiation with 405 and 810 nm pulses (~35 fs) of (1-CAT) induces the formation of an intermediate excited species from which the ground state population is recovered with a time constant of 1.5 ± 0.3 ns. Comparing the 1 ns transient infrared spectrum with the experimental difference spectrum FTIR(2-SQ)-FTIR(1-CAT) and with the calculated difference spectrum IR(c)(1-SQ)-IR(c)(1-CAT) we are able to unequivocally identify the long lived species as the semiquinonate redox isomer of (1). On the other hand, no evidence of photoconversion is observed upon irradiation of (2) with 405 nm. Temporal evolution of transient spectra was analyzed with the combined approach consisting of singular values decomposition and global fitting (global analysis). After 405 and 810 nm excitation of (1-CAT), the semiquinonate excited species is formed on an ultrafast time scale (<200 fs) and cools down within the first 50 ps. Excitation of (2-SQ) with 405 nm wavelength produces a short lived excited state in which the semiquinonate nature of dioxolene is preserved and the ground state recovery is completed within 30 ps.

Second-harmonic-generation (SHG) microscopy has emerged as a powerful tool to image unstained living tissues and probe their molecular and supramolecular organization. In this article, we review the physical basis of SHG, highlighting how coherent summation of second-harmonic response leads to the sensitivity of polarized SHG to the three-dimensional distribution of emitters within the focal volume. Based on the physical description of the process, we examine experimental applications for probing the molecular organization within a tissue and its alterations in response to different biomedically relevant conditions. We also describe the approach for obtaining information on molecular conformation based on SHG polarization anisotropy measurements and its application to the study of myosin conformation in different physiological states of muscle. The capability of coupling the advantages of nonlinear microscopy (micrometer-scale resolution in deep tissue) with tools for probing molecular structure in vivo renders SHG microscopy an extremely powerful tool for the advancement of biomedical optics, with particular regard to novel technologies for molecular diagnostic in vivo.

Two-photon spectral resolved imaging was used to image fresh human biopsies of colon tissue and to characterize healthy colon mucosa, adenomatous polyp and adenocarcinoma by means of a morpho-functional analysis. Morphological examination, performed using endogenous tissue fluorescence, discriminated adenomatous and adenocarcinoma tissues from normal mucosa in terms of cellular asymmetry and nucleus-to-cytoplasm ratio. Good agreement was found between multiphoton images and histological examination performed on the same samples. Further characterization, performed by means of spectral-resolved analysis of NADH and FAD fluorescence, demonstrated an altered metabolic activity in both adenomatous and adenocarcinoma tissues compared to healthy mucosa. This morpho-functional approach may represent a powerful method to be used in combination with endoscopy for in vivo optical diagnosis of colon cancer and may be extended to other tissues.

In this article we present a potential of mean force estimator based on measurements of the work performed on a system during out of equilibrium realizations of a process. More specifically, the quantities involved in the estimator are the work exponential averages related to the forward and backward directions of the process and the free energy difference between the end states. Such free energy difference can be estimated without resorting to additional methodologies or data, but exploiting the available work measurements in the Bennett acceptance ratio method. Despite the fact that work exponential averages give strongly biased free energy profiles, a simple combination of them, supplied with an accurate estimate of the free energy difference between the end states, provides good free energies, even for fast pulling velocities of the control parameter. Numerical tests have been performed on a deterministic non-Hamiltonian dynamic system (the folding/unfolding process of one alanine deca-peptide) and on a stochastic toy model (a particle which moves into a one-dimensional potential according to Langevin dynamics). In these tests we compare our potential of mean force estimator to the unidirectional Jarzynski equality and to other bidirectional estimators that have appeared in the literature recently.

The adsorption of pyridine onto silver colloids has been investigated by Raman spectroscopy experiments and by ab initio DFT and MP2 calculations. The solvation dynamics of the pyridine in water has been studied by a molecular dynamics simulation. The results are compared with the latest available experimental and theoretical data. It is found that the pyridine is essentially hydrogen bonded to one solvent molecule. Calculations based on pyridine-water and pyridine-Ag(+) complexes allow the reproduction of the experimentally observed Raman features and explain the adsorption process of the ligand in silver hydrosols.

Nanocrystals – your flexible friends! The use of nanocrystals as precursors for the one-step formation of flexible functional films by using an air plasma is demonstrated. This treatment does not harm the photoluminescence of the individual nanocrystal building blocks but confers on them resilience to bending as well as acidic environments, hot solvents, annealing, and UV irradiation. The chemical accessibility and selective etching of the nanocrystals allows for micrometer-scale patterning of the film (see Figure).

A surface‐enhanced Raman spectroscopy (SERS) substrate made of agar gel coupled with silver nanoparticles has been applied to the micro‐extraction and the ultra‐sensitive detection of dyes on pieces of textile of different nature (silk, wool, and printed cotton) and on a mock‐up panel painting. In particular, the Ag‐agar gel substrate previously developed has been improved by the addition of the chelating agent ethylenediaminetetraacetic acid (EDTA), which has been found to play an important role as a stabilizer of the nanocomposite matrix and for the improvement of the micro‐extractive performances of the gel. The system has been confirmed to be non‐destructive and minimally invasive, showing a better capability of trapping the dye molecules inside its structure. Ag‐agar gel‐EDTA has been an invaluable and powerful tool for the characterization of the dye present in a printed cotton sample of unknown chemical composition. SERS analyses, performed on the dried cube of gel following extraction on the sample, have allowed for the identification of the dye. SERS results have been corroborated by high‐performance liquid chromatography analyses. The possibility of easily detecting compounds at very low concentration coupled with the high sensitivity of SERS makes this technique a valid and versatile method for the non‐destructive recognition of chemicals in works of art. Copyright © 2014 John Wiley &amp; Sons, Ltd.