Spatially resolved concentration studies of ground state atoms and ions in an ICP: saturated absorption spectroscopic method

The saturated absorption spectroscopic method allows the direct determination of spatial distributions of absorbing species m a plasma to be made. Unlike most other emission and absorption methods which assume radial symmetry and require tedious Abel inversions, this method can be used regardless of the plasma symmetry because of its high spatial resolution. These characteristics are demonstrated with a 27.2 MHz ICP, utilizing short and long torches at power levels of 1.25 kW and 500 W for emission and fluorescence configurations, respectively. Distributions of Sr ground state atoms as well as Ba ground state ions were obtained under various conditions, using a single pulsed dye laser output as the spectroscopic probe in this diagnostic method.     

Spatially resolved NMR thermometry of an operating fixed-bed catalytic reactor

An MRI-based approach for the thermometry of an operating packed-bed catalytic reactor was implemented. It was employed for the spatially resolved NMR thermometry of the bed of Pd/gamma-Al2O3 catalyst beads in the course of propylene hydrogenation reaction. This was achieved by detecting the spatially resolved axial 1D profiles of the 27Al NMR signal intensity of Al2O3 in the course of the reaction. The experimental results demonstrate a clear correlation between the 27Al NMR signal intensity and the catalyst temperature measured with a thermocouple (25-250 degrees C), and reveal the existence of pronounced temperature gradients along the catalyst bed.     

Spatially resolved spectroscopic measurements of a dielectric barrier discharge plasma jet applicable for soft ionization

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry and as ionization source for ion mobility spectrometry. It turned out that dielectric barrier discharge ionization could be regarded as a soft ionization technique characterized by only minor fragmentation similar to atmospheric pressure chemical ionization (APCI). Mainly protonated molecules were detected. In order to characterize the soft ionization mechanism spatially resolved optical emission spectrometry (OES) measurements were performed on plasma jets burning either in He or in Ar. Besides to spatial intensity distributions of noble gas spectral lines, in both cases a special attention was paid to lines of N₂⁺ and N₂. The obtained mapping of the plasma jet shows very different number density distributions of relevant excited species. In the case of helium plasma jet, strong N₂⁺ lines were observed. In contrast to that, the intensities of N₂ lines in Ar were below the present detection limit. The positions of N₂⁺ and N₂ distribution maxima in helium indicate the regions where the highest efficiency of the water ionization and the protonation process is expected.     

Spatially resolved concentration studies of ground state atoms in a flame: saturated absorption spectroscopic method

The authors describe the application of the saturated absorption spectroscopic method, introduced by Goldsmith, Optics Letters6, 525 (1981), to the determination of spatially resolved concentrations of ground state atoms in a flame. In the described version of the method, the beam of a single pulsed dye laser is divided into a probing and a disturing (= saturating beam), which intersect in a small volume of the flame. The perturbance of the probing beam by the saturating beam is a function of the concentration of the absorbing species. The authors foresee this method to become an important tool for flame and plasma diagnostic studies.     

Spatially resolved (semi)quantitative determination of iron (Fe) in plants by means of synchrotron micro X-ray fluorescence

Iron (Fe) is an essential element for plant growth and development; hence determining Fe distribution and concentration inside plant organs at the microscopic level is of great relevance to better understand its metabolism and bioavailability through the food chain. Among the available microanalytical techniques, synchrotron μ-XRF methods can provide a powerful and versatile array of analytical tools to study Fe distribution within plant samples. In the last years, the implementation of new algorithms and detection technologies has opened the way to more accurate (semi)quantitative analyses of complex matrices like plant materials. In this paper, for the first time the distribution of Fe within tomato roots has been imaged and quantified by means of confocal μ-XRF and exploiting a recently developed fundamental parameter-based algorithm. With this approach, Fe concentrations ranging from few hundreds of ppb to several hundreds of ppm can be determined at the microscopic level without cutting sections. Furthermore, Fe (semi)quantitative distribution maps were obtained for the first time by using two opposing detectors to collect simultaneously the XRF radiation emerging from both sides of an intact cucumber leaf.

Spatially resolved single-molecule profiling of microRNAs in migrating cells driven by microconfinement

Cancer cells utilize a range of migration modes to navigate through a confined tissue microenvironment in vivo, while regulatory roles of key microRNAs (miRNAs) remain unclear. Precisely engineered microconfinement and the high spatial-resolution imaging strategy offer a promising avenue for deciphering the molecular mechanisms that drive cell migration. Here, enzyme-free signal-amplification nanoprobes as an effective tool are developed for three-dimensional (3D) high-resolution profiling of key miRNA molecules in single migrating cells, where distinct migration modes are precisely driven by microconfinement-engineered microchips. The constructed nanoprobes exhibit intuitive and ultrasensitive miRNA characterization in vitro by virtue of a single-molecule imaging microscope, and the differential expression and intracellular locations in different cell lines are successfully monitored. Furthermore, 3D spatial distribution of miR-141 at high resolution in flexible phenotypes of migrating cells is reconstructed in the engineered biomimetic microenvironment. The results indicate that miR-141 may be involved in the metastatic transition from a slow to a fast migration state. This work offers a new opportunity for investigating regulatory mechanisms of intracellular key biomolecules during cell migration in biomimetic microenvironments, which may advance in-depth understanding of cancer metastasis in vivo.

Spatially resolved profiling of miRNAs was realized in migrating cells using enzyme-free signal-amplification nanoprobes, in which distinct migration modes of single living cells are driven by precisely engineered microchips.     

The investigation of argon plasma surface modification to polyethylene: Quantitative ATR-FTIR spectroscopic analysis

This paper studied the surface modification of argon plasma to polyethylene by using ATR-FTIR analysis. The mass loss ratio has maximum value at discharge time of 70-120 s or discharge power of 62 W by using argon plasma treatment for polyethylene. New surface structure was formed after polyethylene was treated by argon plasma. The peroxide bond peak area also has maximum value at discharge time of 70-120 s or discharge power of 62 W. The CC nonsaturated double bond absorb peaks were appeared at 1640 cm⁻¹, 1549 cm⁻¹ and 1528 cm⁻¹ after polyethylene treated by argon plasma. The CC nonsaturated double bond absorb peak area has minimum value at discharge time of 60-70 s and the power of 65 W. The CC nonsaturated double bond absorb peak area has maximum value at discharge power of 62-72 W and the discharge time of 2 min. The absorption peak intensity of 2916 cm⁻¹ methylene nonsymmetry stretch vibration, 2848 cm⁻¹ methylene symmetry stretch vibration, 1463 cm⁻¹ methylene nonsymmetry changing angle vibration, and 719 cm⁻¹ methylene swing in plane vibration was decreased greatly. The four absorption peaks intensity has maximum value at discharge time of 120 s or discharge power of 62 W.     

Plasma diagnostics of the barrier discharge in humid argon by cross-correlation spectroscopy

Results of plasma diagnostics of the barrier discharge in humid argon are presented that were obtained by means of the method of cross-correlation spectroscopy. The emission spectrum of the barrier discharge in humid argon was determined. The development of a microdischarge in the system being considered is demonstrated to occur via a multiphase mechanism. The metastables of argon are shown to play a key role in this process.     

Spatially resolved measurements of ion density behind the skimmer of an inductively coupled plasma mass spectrometer

Ions are extracted from the inductively coupled plasma through a conventional sampler and skimmer and then deposited on an array of graphite targets at the exit of a set of electrostatic ion lenses. The Sc⁺ signal is enhanced by choosing appropriate potentials on the ion lenses. The Sc⁺ signal is suppressed by the presence of concomitant Cs ions at high concentrations. Comparisons of grounded ion lenses and two different ion lens potential settings are made. The signal is enhanced more extensively by the ion lenses when there are no concentrated concomitant ions. This study indicates that matrix effects in inductively coupled plasma mass spectrometry could possibly be alleviated by choosing ion lens potentials such that the ions enter the ion optics with a relatively broad beam cross section, the beam then being focused to a smaller size. A photon stop inside the ion lens stack reduces ion transmission and changes the shape of the beam profile from conical to bimodal.     

Spatially controlled cell adhesion via micropatterned surface modification of poly(dimethylsiloxane)

Spatial control of cell growth on surfaces can be achieved by the selective deposition of molecules that influence cell adhesion. The fabrication of such substrates often relies upon photolithography and requires complex surface chemistry to anchor adhesive and inhibitory molecules. The production of simple, cost-effective substrates for cell patterning would benefit numerous areas of bioanalytical research including tissue engineering and biosensor development. Poly(dimethylsiloxane) (PDMS) is routinely used as a biomedical implant material and as a substrate for microfluidic device fabrication; however, the low surface energy and hydrophobic nature of PDMS inhibits its bioactivity. We present a method for the surface modification of PDMS to promote localized cell adhesion and proliferation. Thin metal films are deposited onto PDMS through a physical mask in the presence of a gaseous plasma. This treatment generates topographical and chemical modifications of the polymer surface. Removal of the deposited metal exposes roughened PDMS regions enriched with hydrophilic oxygen-containing species. The morphology and chemical composition of the patterned substrates were assessed by optical and atomic force microscopies as well as X-ray photoelectron spectroscopy. We observed a direct correlation between the surface modification of PDMS and the micropatterned adhesion of fibroblast cells. This simple protocol generates inexpensive, single-component substrates capable of directing cell attachment and growth.     

Microwave plasma in argon produced by a surface wave: study of the effect of pressure on the optical emission and the potentials for analysis of gaseous samples

The possibility of chemical analysis of gaseous samples by optical emission spectroscopy has been evaluated using a microwave induced plasma created by a surface wave at 210 MHz. Methane has been introduced at low concentration (1–20 ppm) in argon gas. The emission of excited CH, CN, C₂ at atmospheric pressure, was observed along the discharge and studied as a function of the methane concentration. The influence of the pressure on CH emission is presented from 10 Torr to atmospheric pressure. Contrary to usual predictions, the emission of CH bands is maximum at about 100 Torr and not at atmospheric pressure.     

New infrared spectroscopic observation of 1,1-dimethyl-1-silaethylene in an argon matrix

Conclusions The pyrolysis of 1,1,3-trimethyl-1-silacyclobutane in vacuo gave 1,1-dimethyl-1-silaethylene, which was stabilized in an argon matrix at 10°K, and its most intense IR absorption bands were recorded: 643.0, 825.2, 1003.5 cm^–1, which coincide exactly with the IR spectrum of the same particle when obtained by the pyrolysis of 1,1-dimethyl-1-silacyclobutane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2152–2153, September, 1979.     

Infrared spectroscopic study of stereo-controlled poly(N-isopropylacrylamide) with an extended chain conformation induced by adsorption on a gold surface

Poly(N-isopropylacrylamide) (PNiPAM) compounds with various diad tacticities were prepared, and the molecular interaction properties in a thin film deposited on a gold surface were analyzed using infrared spectroscopy. The intramolecular and intermolecular interactions were found to depend on the tacticity, and only atactic (diad ratio 46 %) PNiPAM exhibits poor molecular interaction even in the bulk sample. On the other hand, the same series of compounds dissolved in an acetone solution were spread on a gold surface to form a thin film. In the dissolution process, the polymer molecules are relaxed via solvation, and they are bound to the gold surface by a molecular interaction to form a submonolayer thin film. In the thin film, the molecular interaction with the gold surface via the N–H group was monitored in the infrared spectra only for a nearly isotactic (m?=?90) PNiPAM by an apparent shift of the N–H stretching vibration band. This shift was confirmed by changing the degree of hydrophilicity of the gold surface: a larger shift is found on a gold surface with stronger hydrophilicity. As a result, the conformation of a nearly isotactic molecule is found to be extended by the interaction with the gold surface, which works to immobilize the molecule.     

Spatially resolved spectroscopy and structurally encoded imaging by magnetic resonance force microscopy of quadrupolar spin systems

Enhancement of the sensitivity of magnetic resonance force microscopy allowed the extension of the technique to observe half-integer quadrupolar nuclei. This is demonstrated for various different compounds and nuclei with different spin numbers. The possibility of obtaining spatially localized spectral information through the quadrupole interaction is implemented by using nutation NMR. This enables us to superimpose a contrast function on the image of materials depending on their local lattice structure. This opens up new possibilities for both surface and subsurface studies in materials chemistry.     

Plasma diagnostics of barrier-torch discharge in argon flow in a capillary by cross-correlation spectroscopy

The radiation kinetics of the plasma of barrier-torch disrcharge in argon flow in a capillary has been studied by cross-correlation spectroscopy. It was established that the discharge emission spectrum consists of peaks of electronically excited states of argon, bands of hydroxyl radicals, and a second positive system of nitrogen. An analysis of the spatio-temporal distributions of emission intensity for the selected spectral indicators showed that the causes of the torch are ionization waves that extend through the capillary from the electrode system with a speed of 10⁵ m/s and project up to 3–4 mm. It was established that the formation of electronically excited molecules of nitrogen N₂(C ³Π _u ) in the torch of discharge occurs mainly on the reaction between metastable electronically excited atoms of argon and molecules of nitrogen in the electronic ground state.     

Spatially resolved determination of the structure and composition of diatom cell walls by Raman and FTIR imaging

Vibrational spectroscopic imaging has developed into a versatile tool to study the local composition of various materials. Here, we present for the first time that Raman mapping and Fourier transform infrared imaging are useful tools to study diatom cell walls as is demonstrated for the species Stephanopyxis turris. The unicellular diatoms exhibit intricately micro- and nano-patterned cell walls, which consist of amorphous silica as well as various organic and inorganic constituents, thus making up an extremely interesting inorganic/organic hybrid material. The structure and composition of this material as well as the biochemical and biophysical processes leading to its formation remain to be challenges for ongoing research. Whereas the lateral resolution of Fourier transform infrared imaging is limited to 5 μm by diffraction, Raman maps are shown to be capable of detecting the spatial distribution of the silica as well as an additional inorganic component and the organic material down to 330-nm resolution. Due to the spherical shape of the sample with a radius of 40 μm and the requirement to accurately focus the laser before each Raman measurement within the micrometer range, Raman maps of whole diatom cell walls were registered after an adjustment of the axial position. The results reveal local differences in the cell wall composition of the honeycomb-like structures and the bottom layer.     

Geometrical,spectroscopic, and magnetic properties of an oxygen atom adsorbed on the Ni(100) surface

Spin-polarized linear combinations of Gaussian-type orbital–model core potential–local spin density (LCGTO –MCP –LSD ) computations have been performed for oxygen chemisorption on a Ni(100) surface simulated by four different clusters. Results show that the oxygen atom chemisorbs preferentially on the fourfold hollow site with an equilibrium distance of 1.931 Å and a vertical vibrational frequency of 401 cm^?1. The corresponding experimental values are 1.960 Å and 423 or 430 cm^?1. A satisfactory agreement with experiment is also found for the adsorption energy (6.7 vs. 5.6 eV). The bridge position lies at only 0.4 eV above the fourfold hollow one. It is found that oxygen adsorption leaves the bare cluster total spin magnetic moment unchanged, but induces appreciable reductions of the local atomic moment on the surface nickel atoms. © 1993 John Wiley & Sons, Inc.     

A collisional-radiative model including radiation trapping and transport phenomena for diagnostics of an inductively coupled argon plasma

The collisional-radiative model including radiation trapping and transport phenomena along with electron impact and radiative processes has been extended to the actual argon ICP, i.e. structural and inhomogeneous. The electron temperature (T_e), which is an essential plasma parameter for the collisional-radiative model, was measured from the background continuum without assuming the thermal equilibrium between the higher excited atomic levels and the ionic ground state. Observed T_e at the height of 15 mm above the load coil was 8400 K, which was rather lower compared with the literature values determined from the ratio of Ar emission line and continuum in a 40-MHz ICP, while the electron number density was approx. twice larger. The calculated population number densities showed close values to LTE, because the radiation trapping, not only for the resonance lines but also for non-resonance lines, compensated for the overpopulation of low lying levels which might be caused by spontaneous emission. The transport effect of species was negligible in the normal analytical region. In the coaxial zone around 5 mm above the load coil and in the tail flame of the plasma, however, the large inflow of electrons and ions by ambipolar diffusion or convection reduced the number density of argon neutral atoms, where the argon ICP can be denned as a recombining plasma.