We report femtosecond Laser-induced Breakdown Spectroscopy (fs-LIBS) measurements on several amino acids (Serine, Glutamine, and Cysteine) and Albumin protein solutions mixed with Ficoll polysaccharide at different proportions. The goal is to assess the effects of a host matrix on the identification and spectral characterization of amino acids by fs-LIBS. fs-LIBS utilizes an intense short laser pulse to obliterate a sample into basic constituents and to record the emission spectrum of atoms, ions, and molecules in the cooling down of the plasma plume. Several spectral peaks associated primarily with elemental composition of a sample were observed in the fs-LIBS spectra in a range from 200 to 950 nm. In addition, some molecular information associated with diatomic vibrational modes in certain molecules such as C-C and C-N were also obtained. The presence of Ficoll affects the relative intensity and broadening of the CN band, which could be considered as signatures of the amino acids. The fs-LIBS data and their analysis compare favorably with those derived from Fourier Transform Infrared Spectroscopy (FTIR). Interpretation of the spectral information enclosed in the emission of the diatomic molecules during laser ablation may lead to a better understanding of plume chemistry with a direct consequence on chemical analysis of complex samples such as amino acids. Altogether, the results demonstrate the potential of fs-LIBS technique as a detection method of biomolecules and for probing interactions of these biomolecules with a host matrix.
Pyroelectric detector is a class of thermal detector in which the change in temperature causes the change in the spontaneous polarization in the sensing material. In this work, we report the design of uncooled pyroelectric detectors which utilized a nanometer sized truss to support the suspended detector. The design and performance of pyroelectric detectors have been conducted by simulating the structure with Intellisuite™ utilizing Finite Element Method (FEM). The simulated detectors had a spider web-like structure with each of the strut of spider web had a width of 100 nm. Ca modified lead titanate (PCT) was employed as the thermometer because of its high pyroelectric figure of merit. The pyroelectric detectors utilized Ni0.8Cr0.2 absorber, PCT sensing layer, Ti electrodes, Al2O3 structural layer to obtain low thermal conductance between the detector and Si substrate. Three different types of pyroelectric detectors were designed and analyzed. The first design had linear electrode and simple spider web support. The value of the thermal conductance of this detector was found to be 3.98×10-8 W/K. The second design had a longer thermal path than the first one and had a thermal conductivity of 2.41×10-8 W/K. The design was optimized for the best result by modifying the shape, dimension and thickness of various layers namely absorber, electrodes, sensing layer and struts. The thermal conductance of the third design was found to be as low as 4.57×10-9 W/K which is significantly lower than previously reported values. The highest calculated detectivity and reponsivity values were 1.15 × 1010 cm Hz1/2/W and 4.9 × 107 V/W respectively.
We report on pump-probe mode-mismatched photothermal lens experiments of metallic nanoparticles water solutions.
We show that metallic nanoparticles colloids exhibit nonlinear absorption effects related to attraction or repulsion forces
that result from the interaction with the electromagnetic radiation. Gold and iron oxide nanoparticles show a double
peak Z-scan shape that is associated to the presence of attraction forces. We calibrate the experiment using the linear
absorption values of the samples obtaining their corresponding nonlinear absorption coefficients.
We report on a mode-mismatched pump-probe photothermal lens experiment aimed at determination of the thermal diffusivity coefficient of optical samples. In the scheme, the probe beam is collimated and the pump beam is focused. Using a Fresnel diffraction approximation, we show that under these conditions the time dependence of the signal does not depend on the Rayleigh parameters and waist positions of the light beams. This fact allows a more simple and reliable calibration of the experiment in comparison to other schemes. We conduct studies on liquid and solid samples that confirm the predictions of the model. Using the proposed method, we measure the thermal diffusivity coefficient of distilled water, ethanol, methanol, chloroform, nitrobenzene, ethylene glycol, and a solid piece of acrylic plastic. The results are in good agreement with previous measurements.
Fast Fourier transform spectroscopy has proved to be a powerful method for study of the secondary structure of proteins
since peak positions and their relative amplitude are affected by the number of hydrogen bridges that sustain this
secondary structure. However, to our best knowledge, the method has not been used yet for identification of proteins
within a complex matrix like a blood sample. The principal reason is the apparent similarity of protein infrared spectra
with actual differences usually masked by the solvent contribution and other interactions. In this paper, we propose a
novel machine learning based method that uses protein spectra for classification and identification of such proteins
within a given sample. The proposed method uses principal component analysis (PCA) to identify most important linear
combinations of original spectral components and then employs support vector machine (SVM) classification model
applied on such identified combinations to categorize proteins into one of given groups. Our experiments have been
performed on the set of four different proteins, namely: Bovine Serum Albumin, Leptin, Insulin-like Growth Factor 2
and Osteopontin. Our proposed method of applying principal component analysis along with support vector machines
exhibits excellent classification accuracy when identifying proteins using their infrared spectra.
We report on a new application of laser induced breakdown spectroscopy (LIBS) for the diagnosis of diseases such as
ovarian cancer. We perform detection of ovarian cancer biomarker CA 125 based on LIBS measurements. Immunoconjugated
Silicon particles are incubated with the affinity agarose beads carrying CA125 molecules. In the competitive
affinity method Si particles carrying IgG molecules are pre-incubated with CA125. This pre-incubation decreases the
numbers of free IgG molecules available for consequent interaction with the affinity beads. Thus less Si particles are
attached to the agarose beads and consequently smaller Si peak area is measured by LIBS. We demonstrate a limit-ofdetection
about 30 ppb for model protein avidin. We use two-element coded micro-particles to yield spectroscopic
emission code using LIBS. We show that LIBS-based data collecting technique provides methodology for identification
of biomarkers and cost-effective device for future clinical applications.
We report on Fourier transform spectra of deuterated proteins: Bovine Serum Albumin, Leptin, Insulin-like Growth
Factor II, monoclonal antibody to ovarian cancer antigen CA125 and Osteopontin. The spectra exhibit changes in
the relative amplitude and spectral width of certain peaks. New peaks not present in the non-deuterated sample are
also observed. Ways for improving the deuteration of proteins by varying the temperature and dilution time are
discussed. We propose the use of deuterated proteins to increase the sensitivity of immunoassays aimed for early
diagnostic of diseases most notably cancer.
We report on a pump-probe photothermal lens experiment aimed for the measurement of thermal diffusivity
coefficient of organic samples in the CW regime. We show that when the probe beam is collimated and the pump
beam is focused the time dependence of the signal does not depend on the sample position. This effect allows simple
determination of the thermal diffusivity coefficient and its effective calibration using reference samples. We use this
method to determine the thermal diffusivity of distilled water, methanol, chloroform, nitrobenzene and other organic
solvents.
We report on laser-induced breakdown spectroscopy (LIBS) of whole blood and other organic fluids. LIBS spectra, in
the region 200-970 nm, are measured by recording the radiation emitted by the samples following their ablation in a
helium environment. We show that these spectra, although very complex, reveal the presence of elements such as
nitrogen, hydrogen, oxygen and carbon and that of important metallic elements such as iron, magnesium, calcium,
potassium, and sodium. We compare the measured LIBS spectra of whole blood to that of pure carbon and pure iron
and find that in the 200-300 nm region. Nearly 90% of the peaks can be assigned to only these two elements. We also
report on similar studies of methanol, ethanol, isopropanol and water solutions of protein molecules of interest to cancer
research. We show that using simple numerical algorithms, it is possible to distinguish between complex organic
compounds that have nearly the same chemical composition.
We present a two-beam mode-mismatched thermal lens method for pulse excitation aimed for the
determination of one- and two-photon absorption coefficient with high sensitivity. In this scheme the
excitation beam is focused onto the sample in the presence of a collimated CW probe light of low power. The
Z-scan signature is single peaked with a width that depends on the number of photons involved in the
absorption. We show that the method is at least two orders of magnitude more sensitive than the well-known
open Z-scan transmission method commonly used for multi-photon absorption measurement. Using the proposed method we measure a two photon absorption coefficient for nitrobenzene of β=1.12 10-10 cm/W for nanosecond pulses and a wavelength of 532 nm.
Two issues which limit continuous wave second harmonic generation in quasi phase matched KTiOPO4 periodically segmented waveguides are discussed. The first is the thermal loading caused by the fundamental and the second harmonic beams which degrades the quasi-phase matching condition and as a result corrupts the spectral quality of the second-harmonic field. We show that a carefully designed external temperature gradient leads to an enhancement of the conversion efficiency and control of the spectral lineshape of the output field. The second issue discussed is the poor optical coupling into quasi phase matched periodically segmented waveguides. We show that using optical interference, it is possible to increase th efficiency of the generated second harmonic significantly over coupling a single beam with the same total power. Finally, we show that using optical interference, it is also possible to considerably enhance the optical coupling efficiency into single mode fibers.
We report on a novel pump-probe thermal lens method with nearly collimated beams developed for the measurement of absorption coefficients of the order of 10-9 cm-1. This method allows the us of samples of path- lengths 100 cm and larger.
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