Browsing by Subject "RAMAN-SPECTROSCOPY"

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  • Mattinen, Miika; King, Peter J.; Khriachtchev, Leonid; Heikkilä, Mikko J.; Fleming, Ben; Rushworth, Simon; Mizohata, Kenichiro; Meinander, Kristoffer; Räisänen, Jyrki; Ritala, Mikko; Leskelä, Markku (2018)
    Molybdenum forms a range of oxides with different stoichiometries and crystal structures, which lead to different properties and performance in diverse applications. Herein, crystalline molybdenum oxide thin films with controlled phase composition are deposited by atomic layer deposition. The MoO2(thd)2 and O3 as precursors enable well-controlled growth of uniform and conformal films at 200–275 °C. The as-deposited films are rough and, in most cases, consist of a mixture of α- and β-MoO3 as well as an unidentified suboxide MoOx (2.75 ≤ x ≤ 2.89) phase. The phase composition can be tuned by changing deposition conditions. The film stoichiometry is close to MoO3 and the films are relatively pure, the main impurity being hydrogen (2–7 at-%), with ≤1 at-% of carbon and nitrogen. Post-deposition annealing is studied in situ by high-temperature X-ray diffraction in air, O2, N2, and forming gas (10% H2/90% N2) atmospheres. Phase-pure films of MoO2 and α-MoO3 are obtained by annealing at 450 °C in forming gas and O2, respectively. The ability to tailor the phase composition of MoOx films deposited by scalable atomic layer deposition method represents an important step towards various applications of molybdenum oxides.
  • Gal-Or, Eran; Gershoni, Yaniv; Scotti, Gianmario; Nilsson, Sofia Märta Elisabeth; Saarinen, Jukka Kalle Samuel; Jokinen, Ville Petteri; Strachan, Clare Joanna; Boije af Gennäs, Per Gustav; Yli-Kauhaluoma, Jari Tapani; Kotiaho, Ahti Antti Tapio (2019)
    Additive manufacturing (3D printing) is a disruptive technology that is changing production systems globally. In addition, microfluidic devices are increasingly being used for chemical analysis and continuous production of chemicals. Printing of materials such as polymers and metals is already a reality, but additive manufacturing of glass for microfluidic systems has received minor attention. We characterize microfluidic devices (channel cross-section dimensions down to a scale of 100 mm) that have been produced by additive manufacturing of molten soda-lime glass in tens of minutes and report their mass spectrometric and Raman spectroscopic analysis examples. The functionality of a microfluidic glass microreactor is shown with online mass spectrometric analysis of linezolid synthesis. Additionally, the performance of a direct infusion device is demonstrated by mass spectrometric analysis of drugs. Finally, the excellent optical quality of the glass structures is demonstrated with in-line Raman spectroscopic measurements. Our results promise a bright future for additively manufactured glass microdevices in diverse fields of science.
  • Rautaniemi, Kaisa; Vuorimaa-Laukkanen, Elina; Strachan, Clare J.; Laaksonen, Timo (2018)
    Pharmaceutical scientists are increasingly interested in amorphous drug formulations especially because of their higher dissolution rates. Consequently, the thorough characterization and analysis of these formulations are becoming more and more important for the pharmaceutical industry. Here, fluorescence lifetime-imaging microscopy (FLIM) was used to monitor the crystallization of an amorphous pharmaceutical compound, indomethacin. Initially, we identified different solid indomethacin forms, amorphous and gamma- and alpha-crystalline, on the basis of their time-resolved fluorescence. All of the studied indomethacin forms showed biexponential decays with characteristic fluorescence lifetimes and amplitudes. Using this information, the crystallization of amorphous indomethacin upon storage in 60 degrees C was monitored for 10 days with FLIM. The progress of crystallization was detected as lifetime changes both in the FLIM images and in the fluorescence-decay curves extracted from the images. The fluorescence-lifetime amplitudes were used for quantitative analysis of the crystallization process. We also demonstrated that the fluorescence-lifetime distribution of the sample changed during crystallization, and when the sample was not moved between measuring times, the lifetime distribution could also be used for the analysis of the reaction kinetics. Our results clearly show that FLIM is a sensitive and nondestructive method for monitoring solid-state transformations on the surfaces of fluorescent samples.
  • Palomäki, Emmi A. K.; Yliruusi, Jouko K.; Ehlers, Henrik (2019)
    In this paper, the effect of the gaseous environment on recrystallization of amorphous paracetamol was investigated. The experiments were conducted with a headspace gas consisting of dry air, dry carbon dioxide, dry nitrogen and humid air in four temperatures ranging from 5 degrees C below onset of T-g to 5 degrees C above onset of T-g. The recrystallization was monitored using Raman spectroscopy and subsequent multivariate analysis. In temperatures below onset of T-g, the presence of oxygen delayed the onset of recrystallization, with an increasing delay with lower temperature. When comparing samples exposed to dry headspace gases, the crystallization was fastest below onset of Tg when exposed to nitrogen. Being an inert gas, nitrogen did not seem to interfere with the molecules allowing them to freely find their inherent arrangement, whereas the presence of oxygen delayed the formation of stabile nuclei. Above onset of T-g, no differences in onset of crystallization was detected between dry gas atmospheres. Amorphous paracetamol crystallized to form II in all measurements and the samples did not reach full crystallinity within the duration of the experiments. The results show that the headspace gas has an effect on nucleation in the amorphous sample.
  • Pliatsikas, N.; Karabinaki, O.; Zarshenas, M.; Almyras, G. A.; Shtepliuk, I.; Yakimova, R.; Arvanitidis, J.; Christofilos, D.; Sarakinos, K. (2021)
    In the present work, we elucidate the interplay among energetic bombardment effects in magnetron sputtering and defect generation in two-dimensional (2D) materials. Using deposition of gold (Au) layers on single-layer graphene (SLG) as a model system, we study the effect of pressure-distance (pd) product during magnetron sputtering on the pristine SLG properties. Raman spectroscopy, complemented by X-ray photoelectron spectroscopy, shows that for pd = 8.2 Pa center dot cm, Au layer deposition causes defects in the SLG layer, which gradually diminish and eventually disappear with increasing pd to 82.5 Pa center dot cm. Stochastic and deterministic simulations of the sputtering process, the gas-phase transport, and the interaction of sputtered and plasma species with the substrate surface suggest that defects in SLG primarily emanate from ballistic damage caused by backscattered Ar atoms with energies above 100 eV. With increasing pd, and thereby gas-phase scattering, such high energy Ar species become thermalized and hence incapable of causing atomic displacements in the SLG layer. The overall results of our study suggest that control of backscattered Ar energy is a potential path toward enabling magnetron sputtering for fabrication of multifunctional metal contacts in devices founded upon 2D materials.
  • Kohout, T.; Petrova, E.; Yakovlev, G. A.; Grokhovsky, V.; Penttilä, A.; Maturilli, A.; Moreau, J-G; Berzin, S.; Wasiljeff, J.; Danilenko, I. A.; Zamyatin, D. A.; Muftakhetdinova, R. F.; Heikkilä, M. (2020)
    Context. Shock-induced changes in ordinary chondrite meteorites related to impacts or planetary collisions are known to be capable of altering their optical properties. Thus, one can hypothesize that a significant portion of the ordinary chondrite material may be hidden within the observed dark C/X asteroid population. Aims. The exact pressure-temperature conditions of the shock-induced darkening are not well constrained. Thus, we experimentally investigate the gradual changes in the chondrite material optical properties as a function of the shock pressure. Methods. A spherical shock experiment with Chelyabinsk LL5 was performed in order to study the changes in its optical properties. The spherical shock experiment geometry allows for a gradual increase of shock pressure from similar to 15 GPa at a rim toward hundreds of gigapascals in the center. Results. Four distinct zones were observed with an increasing shock load. The optical changes are minimal up to similar to 50 GPa. In the region of similar to 50-60 GPa, shock darkening occurs due to the troilite melt infusion into silicates. This process abruptly ceases at pressures of similar to 60 GPa due to an onset of silicate melting. At pressures higher than similar to 150 GPa, recrystallization occurs and is associated with a second-stage shock darkening due to fine troilite-metal eutectic grains. The shock darkening affects the ultraviolet, visible, and near-infrared region while changes to the MIR spectrum are minimal. Conclusions. Shock darkening is caused by two distinct mechanisms with characteristic pressure regions, which are separated by an interval where the darkening ceases. This implies a reduced amount of shock-darkened material produced during the asteroid collisions.
  • Bogdan, Anatoli; Molina, Mario J.; Tenhu, Heikki; Loerting, Thomas (2015)
    Calorimetric and optical cryo-microscope measurements of 10-64 wt % citric acid (CA) solutions subjected to moderate (3 K/min) and slow (0.5 and 0.1 K/min) cooling/warming rates and also to quenching/moderate warming between 320 and 133 K are presented. Depending on solution concentration and cooling rate, the obtained thermograms show one freezing event and from one to three liquid-glass transitions upon cooling and from one to six liquid-glass and reverse glass-liquid transitions, one or two freezing events, and one melting event upon warming of frozen/glassy CA/H2O. The multiple freezing events and glass transitions pertain to the mother CA/H2O solution itself and two freeze-concentrated solution regions, FCS1 and FCS2, of different concentrations. The FCS1 and FCS2 (or FCS22) are formed during the freezing of CA/H2O upon cooling and/or during the freezing upon warming of partly glassy or entirely glassy mother CA/H2O. The formation of two FCS1 and FCS22 regions during the freezing upon warming to our best knowledge has never been reported before. Using an optical cryo-microscope, we are able to observe the formation of a continuous ice framework (IF) and its morphology and reciprocal distribution of IF/(FCS1 + FCS2). Our results provide a new look at the freezing and glass transition behavior of aqueous solutions and can be used for the optimization of lyophilization and freezing of foods and biopharmaceutical formulations, among many other applications where freezing plays a crucial role.
  • Heiskanen, Vladimir; Hamblin, Michael R. (2018)
    Photobiomodulation (PBM) is a treatment method based on research findings showing that irradiation with certain wavelengths of red or near-infrared light has been shown to produce a range of physiological effects in cells, tissues, animals and humans. Scientific research into PBM was initially started in the late 1960s by utilizing the newly invented (1960) lasers, and the therapy rapidly became known as low-level laser therapy. It was mainly used for wound healing and reduction of pain and inflammation. Despite other light sources being available during the first 40 years of PBM research, lasers remained by far the most commonly employed device, and in fact, some authors insisted that lasers were essential to the therapeutic benefit. Collimated, coherent, highly monochromatic beams with the possibility of high power densities were considered preferable. However in recent years, non-coherent light sources such as light-emitting diodes (LEDs) and broad-band lamps have become common. Advantages of LEDs include no laser safety considerations, ease of home use, ability to irradiate a large area of tissue at once, possibility of wearable devices, and much lower cost per mW. LED photobiomodulation is here to stay.
  • Wester, Niklas; Mynttinen, Elsi; Etula, Jarkko; Lilius, Tuomas; Kalso, Eija; Kauppinen, Esko I.; Laurila, Tomi; Koskinen, Jari (2019)
    In clinical settings, the dosing and differential diagnosis of the poisoning of morphine (MO) and codeine (CO) is challenging due to interindividual variations in metabolism. However, direct electrochemical detection of these analytes from biological matrices is inherently challenging due to interference from large concentrations of anions, such as ascorbic acid (AA) and uric acid (UA), as well as fouling of the electrode by proteins. In this work, a disposable Nafion-coated single-walled carbon nanotube network (SWCNT) electrode was developed. We show facile electron transfer and efficient charge separation between the interfering anions and positively charged MO and CO, as well as significantly reduced matrix effect in human plasma. The Nafion coating alters the voltammetric response of MO and CO, enabling simultaneous detection. With this SWCNT/Nafion electrode, two linear ranges of 0.05-1 and 1-10 mu M were found for MO and one linear range of 0.1-50 mu M for CO. Moreover, the selective and simultaneous detection of MO and CO was achieved in large excess of AA and UA, as well as, for the first time, in unprocessed human plasma. The favorable properties of this electrode enabled measurements in plasma with only mild dilution and without the precipitation of proteins.
  • Castro, Kepa; Knuutinen, Ulla; Fdez-Ortiz de Vallejuelo, Silvia; Maguregui, Maite; Manuel Madariaga, Juan; Laakso, Raili (2016)
    The paint stratigraphy of the two clock faces from the tower clock of the Government Palace in Helsinki (Finland) was analysed in order to determine their original colour before restoration works. Paint cross-section samples from both clock faces were analysed by confocal Raman microscopy and scanning electron microscopy coupled to an energy dispersive X-ray spectrometer (SEM-EDS). The results revealed the complex superimposition of paint layers applied over the original black colour. FTIR/ATR analyses proved that the original paint was prepared with linseed oil-resin media. Most likely not all of the different layer colours were visible. Some of the layers were likely to have been a primer or for rust protection.