The two-dimensional IR nonlinear spectroscopy of a cyclic penta-peptide in relation to its three-dimensional structure

A form of two-dimensional (2D) vibrational spectroscopy, which uses two ultrafast IR laser pulses, is used to examine the structure of a cyclic penta-peptide in solution. Spectrally resolved cross peaks occur in the off-diagonal region of the 2D IR spectrum of the amide I region, analogous to those in 2D NMR spectroscopy. These cross peaks measure the coupling between the different amide groups in the structure. Their intensities and polarizations relate directly to the three-dimensional structure of the peptide. With the help of a model coupling Hamiltonian, supplemented by density functional calculations, the spectra of this penta-peptide can be regenerated from the known solution phase structure. This 2D-IR measurement, with an intrinsic time resolution of less than 1 ps, could be used in all time regimes of interest in biology.

Study of absorption spectrum and dynamics evaluation of the indocyanine-green first singlet excited state

Excited state absorption and excited state dynamics of indocyanine-green (ICG) dissolved in dymethyl sulfoxide were measured using white-light continuum Z-scan (WLCZScan) and white-light continuum pump-probe (WLCPP) techniques. The excited state absorption spectrum, obtained through Z-scan measurements, revealed saturable absorption (SA) for wavelengths longer than 630 nm, while reverse saturable absorption (RSA) appeared, as indicated by a band at approximately 570 nm. Both processes were modeled by a three-energy-level diagram, from which the excited state cross-section values were determined. SA and RSA were also observed in pump-probe experiments, with a recovery time in the hundreds of picoseconds time scale due to the long lifetime of the first excited state of ICG. Such results contribute to the understanding of ICG optical properties, allowing application in photonics and medicine. Copyright (C) 2010 John Wiley & Sons, Ltd.

Dodecyltrimethylammonium chloride adsorption at the silica/water interface studied by Sum Frequency Generation

La génération des fréquences somme (SFG), une technique spectroscopique spécifique aux interfaces, a été utilisée pour caractériser les changements de la structure macromoléculaire du surfactant cationique chlorure de dodécyltriméthylammonium (DTAC) à l’interface silice/eau dans une plage de pH variant entre 3 et 11. Les conditions expérimentales ont été choisies pour imiter les conditions les plus communes trouvées pendant les opérations de récupération assistée du pétrole. Particulièrement, la silice a été étudiée, car elle est un des composantes des surfaces minérales des réservoirs de grès, et l’adsorption du surfactant a été étudiée avec une force ionique pertinente pour les fluides de la fracturation hydraulique. Les spectres SFG ont présenté des pics détectables avec une amplitude croissante dans la région des étirements des groupes méthylène et méthyle lorsque le pH est diminué jusqu’à 3 ou augmenté jusqu’à 11, ce qui suggère des changements de la structure des agrégats de surfactant à l’interface silice/eau à une concentration de DTAC au-delà de la concentration micellaire critique. De plus, des changements dans l’intensité SFG ont été observés pour le spectre de l’eau quand la concentration de DTAC augmente de 0,2 à 50 mM dans les conditions acide, neutre et alcaline. À pH 3, près du point de charge zéro de la surface de silice, l’excès de charge positive en raison de l’adsorption du surfactant cationique crée un champ électrostatique qui oriente les molécules d’eau à l’interface. À pH 7 et 11, ce qui sont des valeurs au-dessus du point de charge zéro de la surface de silice, le champ électrostatique négatif à l’interface silice/eau diminue par un ordre de grandeur avec l’adsorption du surfactant comme résultat de la compensation de la charge négative à la surface par la charge positive du DTAC. Les résultats SFG ont été corrélés avec des mesures de l’angle de contact et de la tension interfaciale à pH 3, 7 et 11.

Dodecyltrimethylammonium chloride adsorption at the silica/water interface studied by Sum Frequency Generation

La génération des fréquences somme (SFG), une technique spectroscopique spécifique aux interfaces, a été utilisée pour caractériser les changements de la structure macromoléculaire du surfactant cationique chlorure de dodécyltriméthylammonium (DTAC) à l’interface silice/eau dans une plage de pH variant entre 3 et 11. Les conditions expérimentales ont été choisies pour imiter les conditions les plus communes trouvées pendant les opérations de récupération assistée du pétrole. Particulièrement, la silice a été étudiée, car elle est un des composantes des surfaces minérales des réservoirs de grès, et l’adsorption du surfactant a été étudiée avec une force ionique pertinente pour les fluides de la fracturation hydraulique. Les spectres SFG ont présenté des pics détectables avec une amplitude croissante dans la région des étirements des groupes méthylène et méthyle lorsque le pH est diminué jusqu’à 3 ou augmenté jusqu’à 11, ce qui suggère des changements de la structure des agrégats de surfactant à l’interface silice/eau à une concentration de DTAC au-delà de la concentration micellaire critique. De plus, des changements dans l’intensité SFG ont été observés pour le spectre de l’eau quand la concentration de DTAC augmente de 0,2 à 50 mM dans les conditions acide, neutre et alcaline. À pH 3, près du point de charge zéro de la surface de silice, l’excès de charge positive en raison de l’adsorption du surfactant cationique crée un champ électrostatique qui oriente les molécules d’eau à l’interface. À pH 7 et 11, ce qui sont des valeurs au-dessus du point de charge zéro de la surface de silice, le champ électrostatique négatif à l’interface silice/eau diminue par un ordre de grandeur avec l’adsorption du surfactant comme résultat de la compensation de la charge négative à la surface par la charge positive du DTAC. Les résultats SFG ont été corrélés avec des mesures de l’angle de contact et de la tension interfaciale à pH 3, 7 et 11.

Design of surface forces apparatus for tribology studies combined with nonlinear optical spectroscopy

We describe the design, calibration, and performance of surface forces apparatus with the capability of illumination of the contact interface for spectroscopic investigation using optical techniques. The apparatus can be placed in the path of a Nd-YAG laser for studies of the linear response or the second harmonic and sum-frequency generation from a material confined between the two surfaces. In addition to the standard fringes of equal chromatic order technique, which we have digitized for accurate and fast analysis, the distance of separation can be measured with a fiber-optic interferometer during spectroscopic measurements (2 Å resolution and 10 ms response time). The sample approach is accomplished through application of a motor drive, piezoelectric actuator, or electromagnetic lever deflection for variable degrees of range, sensitivity, and response time. To demonstrate the operation of the instrument, the stepwise expulsion of discrete layers of octamethylcyclotetrasiloxane from the contact is shown. Lateral forces may also be studied by using piezoelectric bimorphs to induce and direct the motion of one surface.

Photomultiplier nonlinear response in time-domain laser-induced luminescence spectroscopy

A new procedure to find the limiting range of the photomultiplier linear response of a low-cost, digital oscilloscope-based time-resolved laser-induced luminescence spectrometer (TRLS), is presented. A systematic investigation on the instrument response function with different signal input terminations, and the relationship between the luminescence intensity reaching the photomultiplier and the measured decay time are described. These investigations establish that setting the maximum intensity of the luminescence signal below 0.3V guarantees, for signal input terminations equal or higher than 99.7 ohm, a linear photomultiplier response.

A few selected applications of surface nonlinear optical spectroscopy.

As a second-order nonlinear optical process, sum-frequency generation is highly surface-specific and accordingly has been developed into a very powerful and versatile surface spectroscopic tool. It has found many unique applications in different disciplines and thus provided many exciting new research opportunities in surface and surface-related science. Selected examples are discussed here to illustrate the power of the technique.

Fermi-edge singularities in linear and nonlinear ultrafast spectroscopy

We discuss Fermi-edge singularity effects on the linear and nonlinear transient response of an electron gas in a doped semiconductor. We use a bosonization scheme to describe the low-energy excitations, which allows us to compute the time and temperature dependence of the response functions. Coherent control of the energy absorption at resonance is analyzed in the linear regime. It is shown that a phase shift appears in the coherent control oscillations, which is not present in the excitonic case. The nonlinear response is calculated analytically and used to predict that four wave-mixing experiments would present a Fermi-edge singularity when the exciting energy is varied. A new dephasing mechanism is predicted in doped samples that depends linearly on temperature and is produced by the low-energy bosonic excitations in the conduction band.

Sample-induced RF perturbations in high-field, high-resolution NMR spectroscopy

Conducting dielectric samples are often used in high-resolution experiments at high held. It is shown that significant amplitude and phase distortions of the RF magnetic field may result from perturbations caused by such samples. Theoretical analyses demonstrate the spatial variation of the RF field amplitude and phase across the sample, and comparisons of the effect are made for a variety of sample properties and operating field strengths. Although the effect is highly nonlinear, it tends to increase with increasing field strength, permittivity, conductivity, and sample size. There are cases, however, in which increasing the conductivity of the sample improves the homogeneity of the amplitude of the RF field across the sample at the expense of distorted RF phase. It is important that the perturbation effects be calculated for the experimental conditions used, as they have the potential to reduce the signal-to-noise ratio of NMR experiments and may increase the generation of spurious coherences. The effect of RF-coil geometry on the coherences is also modeled, with the use of homogeneous resonators such as the birdcage design being preferred, Recommendations are made concerning methods of reducing sample-induced perturbations. Experimental high-field imaging and high-resolution studies demonstrate the effect. (C) 1997 Academic Press.

Detection and chemical profiling of medicine counterfeits by Raman spectroscopy and chemometrics

Raman spectroscopy combined with chemometrics has recently become a widespread technique for the analysis of pharmaceutical solid forms. The application presented in this paper is the investigation of counterfeit medicines. This increasingly serious issue involves networks that are an integral part of industrialized organized crime. Efficient analytical tools are consequently required to fight against it. Quick and reliable authentication means are needed to allow the deployment of measures from the company and the authorities. For this purpose a method in two steps has been implemented here. The first step enables the identification of pharmaceutical tablets and capsules and the detection of their counterfeits. A nonlinear classification method, the Support Vector Machines (SVM), is computed together with a correlation with the database and the detection of Active Pharmaceutical Ingredient (API) peaks in the suspect product. If a counterfeit is detected, the second step allows its chemical profiling among former counterfeits in a forensic intelligence perspective. For this second step a classification based on Principal Component Analysis (PCA) and correlation distance measurements is applied to the Raman spectra of the counterfeits.

Linear prediction in optical spectroscopy

A linear prediction procedure is one of the approved numerical methods of signal processing. In the field of optical spectroscopy it is used mainly for extrapolation known parts of an optical signal in order to obtain a longer one or deduce missing signal samples. The first is needed particularly when narrowing spectral lines for the purpose of spectral information extraction. In the present paper the coherent anti-Stokes Raman scattering (CARS) spectra were under investigation. The spectra were significantly distorted by the presence of nonlinear nonresonant background. In addition, line shapes were far from Gaussian/Lorentz profiles. To overcome these disadvantages the maximum entropy method (MEM) for phase spectrum retrieval was used. The obtained broad MEM spectra were further underwent the linear prediction analysis in order to be narrowed.

Conventional and nonconventional Kramers-Kronig analysis in optical spectroscopy

This Master’s Thesis is dedicated to the investigation and testing conventional and nonconventional Kramers-Kronig relations on simulated and experimentally measured spectra. It is done for both linear and nonlinear optical spectral data. Big part of attention is paid to the new method of obtaining complex refractive index from a transmittance spectrum without direct information of the sample thickness. The latter method is coupled with terahertz tome-domain spectroscopy and Kramers-Kronig analysis applied for testing the validity of complex refractive index. In this research precision of data inversion is evaluated by root-mean square error. Testing of methods is made over different spectral range and implementation of this methods in future is considered.

Plasma Polymerised Organic Thin Films-A Study on the Structural, Electrical and Nonlinear Optical Properties for Possible Applications

This proposed thesis is entitled “Plasma Polymerised Organic Thin Films: A study on the Structural, Electrical, and Nonlinear Optical Properties for Possible Applications. Polymers and polymer based materials find enormous applications in the realm of electronics and optoelectronics. They are employed as both active and passive components in making various devices. Enormous research activities are going on in this area for the last three decades or so, and many useful contributions are made quite accidentally. Conducting polymers is such a discovery, and eversince the discovery of conducting polyacetylene, a new branch of science itself has emerged in the form of synthetic metals. Conducting polymers are useful materials for many applications like polymer displays, high density data storage, polymer FETs, polymer LEDs, photo voltaic devices and electrochemical cells. With the emergence of molecular electronics and its potential in finding useful applications, organic thin films are receiving an unusual attention by scientists and engineers alike. This is evident from the vast literature pertaining to this field appearing in various journals. Recently, computer aided design of organic molecules have added further impetus to the ongoing research activities in this area. Polymers, especially, conducting polymers can be prepared both in the bulk and in the thinfilm form. However, many applications necessitate that they are grown in the thin film form either as free standing or on appropriate substrates. As far as their bulk counterparts are concerned, they can be prepared by various polymerisation techniques such as chemical routes and electrochemical means. A survey of the literature reveals that polymers like polyaniline, polypyrrole, polythiophene, have been investigated with a view to studying their structural electrical and optical properties. Among the various alternate techniques employed for the preparation of polymer thin films, the method of plasma polymerisation needs special attention in this context. The technique of plasma polymerisation is an inexpensive method and often requires very less infra structure. This method includes the employment of ac, rf, dc, microwave and pulsed sources. They produce pinhole free homogeneous films on appropriate substrates under controlled conditions. In conventional plasma polymerisation set up, the monomer is fed into an evacuated chamber and an ac/rf/dc/ w/pulsed discharge is created which enables the monomer species to dissociate, leading to the formation of polymer thin films. However, it has been found that the structure and hence the properties exhibited by plasma polymerized thin films are quite different from that of their counterparts produced by other thin film preparation techniques such as electrochemical deposition or spin coating. The properties of these thin films can be tuned only if the interrelationship between the structure and other properties are understood from a fundamental point of view. So very often, a through evaluation of the various properties is a pre-requisite for tailoring the properties of the thin films for applications. It has been found that conjugation is a necessary condition for enhancing the conductivity of polymer thin films. RF technique of plasma polymerisation is an excellent tool to induce conjugation and this modifies the electrical properties too. Both oxidative and reductive doping can be employed to modify the electrical properties of the polymer thin films for various applications. This is where organic thin films based on polymers scored over inorganic thin films, where in large area devices can be fabricated with organic semiconductors which is difficult to achieve by inorganic materials. For such applications, a variety of polymers have been synthesized such as polyaniline, polythiophene, polypyrrole etc. There are newer polymers added to this family every now and then. There are many virgin areas where plasma polymers are yet to make a foray namely low-k dielectrics or as potential nonlinear optical materials such as optical limiters. There are also many materials which are not been prepared by the method of plasma polymerisation. Some of the materials which are not been dealt with are phenyl hydrazine and tea tree oil. The advantage of employing organic extracts like tea tree oil monomers as precursors for making plasma polymers is that there can be value addition to the already existing uses and possibility exists in converting them to electronic grade materials, especially semiconductors and optically active materials for photonic applications. One of the major motivations of this study is to synthesize plasma polymer thin films based on aniline, phenyl hydrazine, pyrrole, tea tree oil and eucalyptus oil by employing both rf and ac plasma polymerisation techniques. This will be carried out with the objective of growing thin films on various substrates such as glass, quartz and indium tin oxide (ITO) coated glass. There are various properties namely structural, electrical, dielectric permittivity, nonlinear optical properties which are to be evaluated to establish the relationship with the structure and the other properties. Special emphasis will be laid in evaluating the optical parameters like refractive index (n), extinction coefficient (k), the real and imaginary components of dielectric constant and the optical transition energies of the polymer thin films from the spectroscopic ellipsometric studies. Apart from evaluating these physical constants, it is also possible to predict whether a material exhibit nonlinear optical properties by ellipsometric investigations. So further studies using open aperture z-scan technique in order to evaluate the nonlinear optical properties of a few selected samples which are potential nonlinear optical materials is another objective of the present study. It will be another endeavour to offer an appropriate explanation for the nonlinear optical properties displayed by these films. Doping of plasma polymers is found to modify both the electrical conductivity and optical properties. Iodine is found to modify the properties of the polymer thin films. However insitu iodine doping is tricky and the film often looses its stability because of the escape of iodine. An appropriate insitu technique of doping will be developed to dope iodine in to the plasma polymerized thin films. Doping of polymer thin films with iodine results in improved and modified optical and electrical properties. However it requires tools like FTIR and UV-Vis-NIR spectroscopy to elucidate the structural and optical modifications imparted to the polymer films. This will be attempted here to establish the role of iodine in the modification of the properties exhibited by the films

Spectral and nonlinear optical characterization of ZnO nanocomposites

The spectral and nonlinear optical characteristics of nano ZnO and its composites are investigated. The fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength and there is a red shift in emission peak with excitation wavelength. Apart from the observation of the reported ultra violet and green emissions, our results reveal that additional blue emissions at 420 nm and 490 nm are developed with increasing particle size. Systematic studies on nano ZnO have indicated the presence of luminescence due to excitonic emissions when excited with 255 nm as well as significant contribution from surface defect states when excited with 325 nm. In the weak confinement regime, the third-order optical susceptibility χ(3) increases with increasing particle size (R) and annealing temperature (T) and a R2 and T2.5 dependence of χ(3) is obtained for nano ZnO. ZnO nanocolloids exhibit induced absorption whereas the self assembled films of ZnO exhibit saturable absorption due to saturation of linear absorption of ZnO defect states and electronic effects. ZnO nanocomposites exhibit negative nonlinear index of refraction which can be attributed to two photon absorption followed by weak free carrier absorption. The increase of the third-order nonlinearity in the composites can be attributed to the enhancement of exciton oscillator strength. The nonlinear response of ZnO nanocomposites is wavelength dependent and switching from induced absorption to saturable absorption has been observed at resonant wavelengths. Such a change-over is related to the interplay of plasmon/exciton band bleach and optical limiting mechanisms. This study is important in identifying the spectral range and the composition over which the nonlinear material acts as an optical limiter. ZnO based nanocomposites are potential materials for enhanced and tunable light emission and for the development of nonlinear optical devices with a relatively small optical limiting threshold.