0000000000049733
AUTHOR
Heikki Häkkänen
Laser-induced plasma spectroscopy in near vacuum ultraviolet using ordinary spectrograph and ICCD
An experimental setup to measure laser-induced plasma emission spectra with an ordinary Czerny-Turner spectrograph and intensified charge-coupled device in the near vacuum ultraviolet down to 130 nm is described. Spectra of bromine, chlorine and iodine were recorded to demonstrate the performance of the setup.
X-ray microtomography and laser ablation in the analysis of ink distribution in coated paper
A novel method was developed for studying the ink-paper interface and the structural variations of a deposited layer of ink. Combining high-resolution x-ray tomography with laser ablation, the depth profile of ink (toner), i.e., its varying thickness, could be determined in a paper substrate. X-ray tomography was used to produce the 3D structure of paper with about 1 μm spatial resolution. Laser ablation combined with optical imaging was used to produce the 3D structure of the printed layer of ink on top of that paper with about 70 nm depth resolution. Ablation depth was calibrated with an optical profilometer. It can be concluded that a toner layer on a light-weight-coated paper substrate …
Time-gated Raman and laser-induced breakdown spectroscopy in mapping of eudialyte and catapleiite
Raman analysis of rock samples containing rare earth elements (REEs) is challenging due to the strong fluorescence, which may mask the weaker Raman signal. In this research, time‐gated (TG) Raman has been applied to the construction of the mineral distribution map from REE‐bearing rock. With TG Raman, material is excited with a short subnanosecond laser pulse, and the Raman signal is collected within a picosecond‐scale time window prior to the formation of a strong fluorescent signal by means of single‐photon avalanche diode array. This allows signal readout with a significantly reduced fluorescence background. TG Raman maps are used to reveal the location of valuable minerals and are compa…
Luminescence study of defects in synthetic as-grown and HPHT diamonds compared to natural diamonds
The optically active defects in as-grown, high-pressure high-temperature-treated (HPHT), boron-doped, and synthetic diamonds (SD) grown with a nitrogen-getter, as well as of natural diamonds (ND), were characterized by absorption and luminescence spectroscopies using different excitation sources. The laser-excited photoluminescence (PL) spectra of SDs show numerous sharp lines characteristic for nickel-related centers, whereas NDs yield mainly broad PL bands. The emission from the nickel-related defects in NIR range increases and the maxima of the bands shift to lower energies with increasing temperature. Under UV and electron beam excitation, the yellow synthetic diamonds display green lum…
Laser-induced time-resolved luminescence in analysis of rare earth elements in apatite and calcite
Laser-induced time-resolved luminescence was used to study rare earth element (REE) containing natural apatite and calcite minerals. The luminescence from 400 nm to 700 nm in the minerals was analyzed with excitation ranges 210–340 nm and 405–535 nm. As an outcome, several useful excitation wavelengths to detect one or more REE from apatite and calcite are reported. The feasibility of selected excitations in e.g. avoiding the disturbance of intense Mn2+ luminescence band, results was demonstrated with a non-gated detector. peerReviewed
Differentiation of natural and synthetic gem-quality diamonds by luminescence properties
Abstract Laser-excited time-resolved and UV-excited static photoluminescence (PL) as well as cathodoluminescence (CL) techniques were applied to identify the origin of diamonds. Samples represented natural faced and rough diamonds from diamond market and different kimberlites as well as the most common high pressure–high temperature (HPHT) and as-grown synthetic diamonds. The time-resolved PL spectra of natural and synthetic diamonds display clear mutual differences. The static PL and CL spectra of natural diamonds revealed emission bands caused by complex nitrogen–vacancy (N–V)-aggregates whereas the bands of synthetic diamonds reflect simple N–V-aggregates and nickel-containing defects. T…
Laser-Induced Breakdown Spectroscopy for Rapid Elemental Analysis of Drillcore
Abstract The elemental and mineralogical contents of rock drillcore can be analyzed using a variety of methods. For efficient exploration the characterization of the drillcore should be performed rapidly, so that the further drillings can be better planned and unnecessary costs can be reduced. In this paper, laser-induced breakdown spectroscopy (LIBS) is studied as a potential rapid on-line method for automated elemental analysis of drillcore. The method is based on a pulsed laser beam that transforms a small volume of the sample into plasma. Individual elements in the plasma have characteristic emission patterns detectable by a spectrometer. Based on the measured spectra the amount of diff…
Determination of Cl/C and Br/C ratios in pure organic solids using laser-induced plasma spectroscopy in near vacuum ultraviolet
Several solid organic compounds containing bromine and chlorine were analyzed with laser-induced plasma spectroscopy. Emission lines were detected in the near vacuum ultraviolet spectral region by using a gas-purged spectrograph and an intensified charge-coupled device detector. The performance of this setup in the determination of the halides in the organic samples was evaluated. Carbon emission lines in the near vacuum ultraviolet were used as internal standards for the measurement of chlorine and bromine. Linear correlation was found between the carbon and halogen emission signal ratio and the corresponding atomic ratio of the compound.
Singular value decomposition approach to the yttrium occurrence in mineral maps of rare earth element ores using laser-induced breakdown spectroscopy
Laser-induced breakdown spectroscopy (LIBS) has been used in analysis of rare earth element (REE) ores from the geological formation of Norra Kärr Alkaline Complex in southern Sweden. Yttrium has been detected in eudialyte (Na15 Ca6(Fe,Mn)3 Zr3Si(Si25O73)(O,OH,H2O)3 (OH,Cl)2) and catapleiite (Ca/Na2ZrSi3O9·2H2O). Singular value decomposition (SVD) has been employed in classification of the minerals in the rock samples and maps representing the mineralogy in the sampled area have been constructed. Based on the SVD classification the percentage of the yttrium-bearing ore minerals can be calculated even in fine-grained rock samples. peerReviewed
Sulfide mineral identification using laser-induced plasma spectroscopy
Sulfide minerals in rock samples were identified with laser-induced plasma spectroscopy (LIPS) in the near vacuum ultraviolet spectral region. Reference spectra of pyrite, pyrrhotite, chalcopyrite, sphalerite, barite, calcite and dolomite were applied to classification of minerals in sulfur-bearing drill core samples. On the basis of the results mineral distributions in the sample were estimated. The potential of the LIPS method for in situ analysis is discussed.
Bioactive glass ions as strong enhancers of osteogenic differentiation in human adipose stem cells.
Bioactive glasses are known for their ability to induce osteogenic differentiation of stem cells. To elucidate the mechanism of the osteoinductivity in more detail, we studied whether ionic extracts prepared from a commercial glass S53P4 and from three experimental glasses (2-06, 1-06 and 3-06) are alone sufficient to induce osteogenic differentiation of human adipose stem cells. Cells were cultured using basic medium or osteogenic medium as extract basis. Our results indicate that cells stay viable in all the glass extracts for the whole culturing period, 14 days. At 14 days the mineralization in osteogenic medium extracts was excessive compared to the control. Parallel to the increased mi…
Bridged Epipolythiodiketopiperazines from Penicillium raciborskii, an Endophytic Fungus of Rhododendron tomentosum Harmaja
Three new epithiodiketopiperazine natural products [outovirin A (1), outovirin B (2), and outovirin C (3)] resembling the antifungal natural product gliovirin have been identified in extracts of Penicillium raciborskii, an endophytic fungus isolated from Rhododendron tomentosum. The compounds are unusual for their class in that they possess sulfide bridges between α- and β-carbons rather than the typical α-α bridging. To our knowledge, outovirin A represents the first reported naturally produced epimonothiodiketopiperazine, and antifungal outovirin C is the first reported trisulfide gliovirin-like compound. This report describes the identification and structural elucidation of the compounds…
Study of Toner Penetration in Papers by Laser Induced Plasma Spectroscopy and Optical Profilometry
Four major toners are used in the printing industry, cyan, magenta, yellow and black (Key) for making color images on paper. Paper brands suitable for printing have thin mineral/latex coatings, and toners are applied on top of the coating in the printing process. Chemical compositions from toner to toner, as well as from coating to coating, vary according to the needs of the end user. Interactions between the toner and the coating define the final color formation of the images in printing. Hence, it is important to study characteristics and dynamics of toners on coated papers. In this paper, we have used laser-induced plasma spectroscopy (LIBS) to provide information on elemental distributi…
Light-induced structural changes in a monomeric bacteriophytochrome
International audience; Phytochromes sense red light in plants and various microorganism. Light absorption causes structural changes within the protein, which alter its biochemical activity. Bacterial phytochromes are dimeric proteins, but the functional relevance of this arrangement remains unclear. Here, we use time-resolved X-ray scattering to reveal the solution structural change of a monomeric variant of the photosensory core module of the phytochrome from Deinococcus radiodurans. The data reveal two motions, a bend and a twist of the PHY domain with respect to the chromophore-binding domains. Infrared spectroscopy shows the refolding of the PHY tongue. We conclude that a monomer of th…
Detection of fluorine using laser-induced breakdown spectroscopy and Raman spectroscopy
In general, the detection of F and other halogens is challenging through conventional techniques. In this paper, various approaches for the qualitative and quantitative analysis of F using the laser-induced breakdown spectroscopy (LIBS) technique were demonstrated. In LIBS, fluorine detection can be realized by means of atomic lines and molecular bands. For the purposes of our experiment, two sets of pellets with various contents of CaF2, CaCO3 and cellulose were analyzed using a lab-based LIBS system under a He atmosphere. The fluorine atomic line at 685.60 nm was correlated with CaF signals proving their close relationship. Consequently, the limits of detection were determined for both an…
X-ray microtomography and laser ablation in the analysis of ink distribution in coated paper
A novel method was developed for studying the ink-paper interface and the structural variations of a deposited layer of ink. Combining high-resolution x-ray tomography with laser ablation, the depth profile of ink (toner), i.e., its varying thickness, could be determined in a paper substrate. X-ray tomography was used to produce the 3D structure of paper with about 1 lm spatial resolution. Laser ablation combined with optical imaging was used to produce the 3D structure of the printed layer of ink on top of that paper with about 70 nm depth resolution. Ablation depth was calibrated with an optical profilometer. It can be concluded that a toner layer on a light-weight-coated paper substrate …
Laser-Induced Plasma Emission Spectrometric Study of Pigments and Binders in Paper Coatings: Matrix Effects
Laser-induced plasma emission spectroscopy (LIPS) has been used to study inorganic pigment and organic binder distributions in paper coatings, which are inhomogeneous and porous materials. The plasma was generated by focusing a pulsed XeCl excimer laser beam (diameter 100 μm, irradiance 0.3 GW/cm2) on the sample surface at atmospheric pressure. A gated intensified CCD detector was used to record time-delayed emission spectra. Linear correlations between the LIPS signals and the coat weight and the binder content of the coatings studied were obtained. Emission line intensities from ionic and neutral magnesium atoms were used to evaluate plasma temperature corrections in determining silicon a…
Laser-Induced Fluorescence Imaging of Paper Surfaces
Laser-induced fluorescence imaging has been used to study the microstructure of paper surfaces. Pulses from a XeCl-excimer laser, 10 ns in duration at 308 nm, were used for excitation, and fluorescence was collected at 420 nm. The excitation spot diameter was approximately 20 µm, and the sampling interval 0.15 mm. Within an area of 5*5 mm2, 1023 sampling points were recorded to generate 3D fluorescence maps of paper surfaces. Papers containing fluorescence whitening agents (FWAs) gave the highest average fluorescence signals. Coated papers with no FW As show weaker signals than the base sheet. For some thirty different paper samples, an obvious correlation between the amount of coating and…
Site-by-site tracking of signal transduction in an azidophenylalanine-labeled bacteriophytochrome with step-scan FTIR spectroscopy
Signal propagation in photosensory proteins is a complex and multidimensional event. Unraveling such mechanisms site-specifically in real time is an eligible but a challenging goal. Here, we elucidate the site-specific events in a red-light sensing phytochrome using the unnatural amino acid azidophenylalanine, vibrationally distinguishable from all other protein signals. In canonical phytochromes, signal transduction starts with isomerization of an excited bilin chromophore, initiating a multitude of processes in the photosensory unit of the protein, which eventually control the biochemical activity of the output domain, nanometers away from the chromophore. By implementing the label in pri…
Enhanced quantification of wollastonite and calcite in limestone using fluorescence correction based on continuous wavelet transformation for Raman
Raman spectroscopy offers a nondestructive means to identify minerals in rocks, but the ability to use the technology for quantitative mineralogical analysis is limited by fluorescence that can mask the spectral features of minerals. In this paper we apply continuous wavelet transformation (CWT) to remove fluoresence from Raman data acquired from 26 carbonate rock samples. We then record the intensity values of individual spectral features, proxies for mineral abundances, using the original Raman data and the thus inferred CWT data. The intensity values are then compared against the known mineral abundances determined using the scanning electron microscope (SEM) technology. This comparison …
Raman Spectroscopic Signatures of Echovirus 1 Uncoating
ABSTRACT In recent decades, Raman spectroscopy has entered the biological and medical fields. It enables nondestructive analysis of structural details at the molecular level and has been used to study viruses and their constituents. Here, we used Raman spectroscopy to study echovirus 1 (EV1), a small, nonenveloped human pathogen, in two different uncoating states induced by heat treatments. Raman signals of capsid proteins and RNA genome were observed from the intact virus, the uncoating intermediate, and disrupted virions. Transmission electron microscopy data revealed general structural changes between the studied particles. Compared to spectral characteristics of proteins in the intact v…
Chromophore-Protein Interplay During the Phytochrome Photocycle Revealed by Step-Scan FTIR Spectroscopy
Phytochrome proteins regulate many photoresponses of plants and microorganisms. Light absorption causes isomerization of the biliverdin chromophore, which triggers a series of structural changes to activate the signaling domains of the protein. However, the structural changes are elusive, and therefore the molecular mechanism of signal transduction remains poorly understood. Here, we apply two-color step-scan infrared spectroscopy to the bacteriophytochrome from Deinococcus radiodurans. We show by recordings in H2O and D2O that the hydrogen bonds to the biliverdin D-ring carbonyl become disordered in the first intermediate (Lumi-R) forming a dynamic microenvironment, then completely detach …
UV-Laser Plasma Study of Elemental Distributions of Paper Coatings
The potential of a laser-generated plasma method in the analysis of coating coverage, coatweight distribution, and 3D distribution of various pigments of paper coating is described. A XeCl-excimer laser (308 nm) was used to generate microscopic plasma from the paper coating, and delayed detection of silicon and calcium atomic emission line intensities was used as a measure of mass vaporized. Macroscopic areas typically 10 × 10 mm2 at a spatial resolution of 250 μm were studied. With a single laser pulse (0.2 mJ of energy), about 2 ng of coating from a volume of 30 μm in diameter and 2 μm in depth was vaporized. The method seems to be useful for characterization of multilayer coatings.
Bioactive glass ions induce efficient osteogenic differentiation of human adipose stem cells encapsulated in gellan gum and collagen type I hydrogels
Abstract Background Due to unmet need for bone augmentation, our aim was to promote osteogenic differentiation of human adipose stem cells (hASCs) encapsulated in gellan gum (GG) or collagen type I (COL) hydrogels with bioactive glass (experimental glass 2-06 of composition [wt-%]: Na2O 12.1, K2O 14.0, CaO 19.8, P2O5 2.5, B2O3 1.6, SiO2 50.0) extract based osteogenic medium (BaG OM) for bone construct development. GG hydrogels were crosslinked with spermidine (GG-SPD) or BaG extract (GG-BaG). Methods Mechanical properties of cell-free GG-SPD, GG-BaG, and COL hydrogels were tested in osteogenic medium (OM) or BaG OM at 0, 14, and 21 d. Hydrogel embedded hASCs were cultured in OM or BaG OM fo…
Laser-induced plasma spectroscopy to as low as 130 nm when a gas-purged spectrograph and ICCD detection are used.
An experimental setup is described for measuring laser-induced plasma emission spectra in the near vacuum UV with a Czerny-Turner spectrograph and intensified charge-coupled device under atmospheric pressure. With a simple gas-purge technique, emission lines down to 130 nm could be recorded. The strongest emission lines of bromine, chlorine, and iodine in the near vacuum UV are easily detected.
Optimisation algorithms in the case of mineral detection using Raman Analysis
Abstract Raman analysis can be used to analyse the existence of minerals in an ore sample. Especially the interest here is to analyse given ore sample rapidly, to find out what minerals it contains. Rapid analysis would enable more rapid exploration of minerals as analysis could be carried out on-site. For this study, ore samples were collected from two mines in Northern Finland, Kittila and Kevitsa. An optimisation algorithm was constructed to form a linear combination of reference spectra which best represent the measured spectrum from an ore sample. The reference spectra were collected from a public source. It was found that solving for an optimal summation of reference spectra can be a …
Laserspektroskopia mineraalianalytiikassa : nopeasti ja tehokkaasti monipuolista informaatiota mineraaleista
Laserspektroskopiset menetelmät ovat nopeita ja tehokkaita mineraalitutkimuksen keinoja, koska analyysi voidaan tehdä suoraan näytteen pinnalta ja jopa metrien päästä kohteesta. Nykyteknologian ansiosta laserspektroskopian laitteistoja voidaan lisäksi miniatyrisoida, ja siten ne soveltuvat etämittauksiin esimerkiksi maastossa, linjastolla tai kaivoksessa (in situ). Tässä artikkelissa esitellään laserindusoitu plasmaspektroskopia (LIBS), laser-indusoitu luminesenssispektroskopia ja Raman-spektroskopia, joilla saadaan näytteistä toisiaan täydentävää informaatiota (Romppanen 2021). Tunnetuimmat esimerkit laserspektroskopian soveltuvuudesta mineraalianalytiikassa löytyvät Marsista, sillä planee…
Optimization of spodumene identification by statistical approach for laser-induced breakdown spectroscopy data of lithium pegmatite ores
Mapping with laser-induced breakdown spectroscopy (LIBS) can offer more than just the spatial distribution of elements: the rich spectral information also enables mineral recognition. In the present study, statistical approaches were used for the recognition of the spodumene from lithium pegmatite ores. A broad spectral range (280–820 nm) with multiple lines was first used to establish the methods based on vertex component analysis (VCA) and K-means and DBSCAN clusterings. However, with a view to potential on-site applications, the dimensions of the datasets must be reduced in order to accomplish fast analysis. Therefore, the capability of the methods in mineral identification was tested wi…
Analysis of paper by laser-induced plasma spectroscopy
Abstract Material distributions in paper and paper coatings are important factors which determine the characteristics and quality of paper. We have used laser-induced plasma spectroscopy (LIPS) to determine various properties of coated and uncoated papers. Depth profiles of double coated papers were determined. Microscopic variations of pigments in a double-coated paper were analyzed. It was observed, that the two coating layers can be distinguished, if they differ enough in composition. Filler distributions of uncoated copier papers were determined. The surface of the paper was studied for five samples containing different amounts of binder in the coating. Lateral contamination in paper an…
Time‐gated Raman and laser‐induced breakdown spectroscopy in mapping of eudialyte and catapleiite
Abstract Raman analysis of rock samples containing rare earth elements (REEs) is challenging due to the strong fluorescence, which may mask the weaker Raman signal. In this research, time‐gated (TG) Raman has been applied to the construction of the mineral distribution map from REE‐bearing rock. With TG Raman, material is excited with a short subnanosecond laser pulse, and the Raman signal is collected within a picosecond‐scale time window prior to the formation of a strong fluorescent signal by means of single‐photon avalanche diode array. This allows signal readout with a significantly reduced fluorescence background. TG Raman maps are used to reveal the location of valuable minerals and …
The Effect of Intense Air Drying on Material Distribution and Quality in Coated Papers
Abstract The aim of this study was to find out what will happen to paper coating quality and material gradients if coating is dried in one air dryer at a high convection rate (150 kg/m2h). Different printing papers were coated, calendered and printed with pilot machines. The binder and pigment gradients of the coated, and also printed, samples were analyzed with LIPS (Laser Induced Plasma Spectrometry). It was found that drying affects the migration of starch, but not latex. Total air drying can be used to dry printing papers, if air temperature, velocity and moisture content can be separately controlled. The control of web temperature is more important for paper quality formation in a coat…
Coordination of the biliverdin D-ring in bacteriophytochromes.
Phytochrome proteins translate light into biochemical signals in plants, fungi and microorganisms. Light cues are absorbed by a bilin chromophore, leading to an isomerization and a rotation of the D-ring. This relays the signal to the protein matrix. A set of amino acids, which is conserved across the phytochrome superfamily, holds the chromophore in the binding pocket. However, the functional role of many of these amino acids is not yet understood. Here, we investigate the hydrogen bonding network which surrounds the D-ring of the chromophore in the resting (Pr) state. We use UV/vis spectroscopy, infrared absorption spectroscopy and X-ray crystallography to compare the photosensory domains…
Enhanced quantification of wollastonite and calcite in limestone using fluorescence correction based on continuous wavelet transformation for Raman
Raman spectroscopy offers a nondestructive means to identify minerals in rocks, but the ability to use the technology for quantitative mineralogical analysis is limited by fluorescence that can mask the spectral features of minerals. In this paper we apply continuous wavelet transformation (CWT) to remove fluoresence from Raman data acquired from 26 carbonate rock samples. We then record the intensity values of individual spectral features, proxies for mineral abundances, using the original Raman data and the thus inferred CWT data. The intensity values are then compared against the known mineral abundances determined using the scanning electron microscope (SEM) technology. This comparison …