Absolute Calibration of Atomic Density Measurements by Laser-Induced Fluorescence Spectroscopy with Two-Photon Excitation (TALIF)

The two-photon resonances of atomic hydrogen (? = 2 × 205.1 nm), atomic nitrogen (? = 2 × 206.6 nm) and atomic oxygen (? = 2 × 225.6 nm) are investigated together with two selected transitions in krypton (? = 2×204.2 nm) and xenon (? = 2×225.5 nm). The natural lifetimes of the excited states, quenching coefficients for the most important collisions partners, and the relevant ratios of the two-photon excitation cross sections are measured. These data can be applied to provide a calibration for two-photon laser-induced fluorescence measurements based on comparisons with spectrally neighbouring noble gas resonances.

Absolute Atomic Oxygen Density Measurements by Two-Photon Absorption Laser-induced Fluorescence Spectroscopy in an RF-Excited Atmospheric Pressure Plasma Jet

The atmospheric pressure plasma jet is a capacitively coupled radio frequency discharge (13.56 MHz) running with a high helium flux (2m3 h-1) between concentric electrodes. Small amounts (0.5%) of admixed molecular oxygen do not disturb the homogeneous plasma discharge. The jet effluent leaving the discharge through the ring-shaped nozzle contains high concentrations of radicals at a low gas temperature—the key property for a variety of applications aiming at treatment of thermally sensitive surfaces. We report on absolute atomic oxygen density measurements by two-photon absorption laser-induced fluorescence (TALIF) spectroscopy in the jet effluent. Calibration is performed with the aid of a comparative TALIF measurement with xenon. An excitation scheme (different from the one earlier published) providing spectral matching of both the two-photon resonances and the fluorescence transitions is applied.

Application of Fluorescence Spectroscopy to Quantify Shear-Induced Protein Conformation Change

Rapid and robust methods are required to quantify the effect of hydrodynamic shear on protein conformation change. We evaluated such strategies in this work and found that the binding of the fluorescent probe 4,4'-dianilino-1, 1'-binaphthyl-5,5'-disulfonic acid (bis-ANS) to hydrophobic pockets in the blood protein von Willebrand factor (VWF) is enhanced upon the application of fluid shear to the isolated protein. Significant structural changes were observed when the protein was sheared at shear rates >= 6000/s for similar to 3.5 min. The binding of bis-ANS to multimeric VWF, but not dimeric VWF or control protein bovine serum albumin, was enhanced upon fluid shear application. Thus, high-molecular-weight VWF is more susceptible to conformation change upon tensile loading. Although bis-ANS itself did not alter the conformation of VWF, it stabilized protein conformation once it bound the sheared molecule. Bis-ANS binding to VWF was reduced when the sheared protein was allowed to relax before dye addition. Taken together with functional data in the literature, our results suggest that shear-induced conformation changes in VWF reported by bis-ANS correlate well with the normal function of the protein under physiological/pathological fluid flow conditions. Further, this study introduces the fluorescent dye bis-ANS as a tool that may be useful in studies of shear-induced protein conformation change.

Laser-Induced Fluorescence Measurements of Absolute Atomic Densities: Concepts and Limitations

The potential of laser-induced fluorescence spectroscopy of atoms is reviewed with emphasis on the determination of absolute densities. Examples of experiments with single-photon and two-photon excitation are presented. Calibration methods applicable with the different schemes are discussed. A new method is presented that has the potential to allow absolute measurement in plasmas of elevated pressure where collisional depletion of the excited state is present.

Neutral gas depletion mechanisms in dense low-temperature argon plasmas

Neutral gas depletion mechanisms are investigated in a dense low-temperature argon plasma-an inductively coupled magnetic neutral loop (NL) discharge. Gas temperatures are deduced from the Doppler profile of the 772.38 nm line absorbed by argon metastable atoms. Electron density and temperature measurements reveal that at pressures below 0.1 Pa, relatively high degrees of ionization (exceeding 1%) result in electron pressures, p(e) = kT(e)n(e), exceeding the neutral gas pressure. In this regime, neutral dynamics has to be taken into account and depletion through comparatively high ionization rates becomes important. This additional depletion mechanism can be spatially separated due to non-uniform electron temperature and density profiles (non-uniform ionization rate), while the gas temperature is rather uniform within the discharge region. Spatial profiles of the depletion of metastable argon atoms in the NL region are observed by laser induced fluorescence spectroscopy. In this region, the depletion of ground state argon atoms is expected to be even more pronounced since in the investigated high electron density regime the ratio of metastable and ground state argon atom densities is governed by the electron temperature, which peaks in the NL region. This neutral gas depletion is attributed to a high ionization rate in the NL zone and fast ion loss through ambipolar diffusion along the magnetic field lines. This is totally different from what is observed at pressures above 10 Pa where the degree of ionization is relatively low (

Diagnostics on an atmospheric pressure plasma jet

The atmospheric pressure plasma jet (APPJ) is a homogeneous non-equilibrium discharge at ambient pressure. It operates with a noble base gas and a percentage-volume admixture of a molecular gas. Applications of the discharge are mainly based on reactive species in the effluent. The effluent region of a discharge operated in helium with an oxygen admixture has been investigated. The optical emission from atomic oxygen decreases with distance from the discharge but can still be observed several centimetres in the effluent. Ground state atomic oxygen, measured using absolutely calibrated two-photon laser induced fluorescence spectroscopy, shows a similar behaviour. Detailed understanding of energy transport mechanisms requires investigations of the discharge volume and the effluent region. An atmospheric pressure plasma jet has been designed providing excellent diagnostics access and a simple geometry ideally suited for modelling and simulation. Laser spectroscopy and optical emission spectroscopy can be applied in the discharge volume and the effluent region.

Spatially resolved diagnostics on a micro atmospheric pressure plasma jet

Despite enormous potential for technological applications, fundamentals of stable non-equilibrium micro-plasmas at ambient pressure are still only partly understood. Micro-plasma jets are one sub-group of these plasma sources. For an understanding it is particularly important to analyse transport phenomena of energy and particles within and between the core and effluent of the discharge. The complexity of the problem requires the combination and correlation of various highly sophisticated diagnostics yielding different information with an extremely high temporal and spatial resolution. A specially designed rf microscale atmospheric pressure plasma jet (µ-APPJ) provides excellent access for optical diagnostics to the discharge volume and the effluent region. This allows detailed investigations of the discharge dynamics and energy transport mechanisms from the discharge to the effluent. Here we present examples for diagnostics applicable to different regions and combine the results. The diagnostics applied are optical emission spectroscopy (OES) in the visible and ultraviolet and two-photon absorption laser-induced fluorescence spectroscopy. By the latter spatially resolved absolutely calibrated density maps of atomic oxygen have been determined for the effluent. OES yields an insight into energy transport mechanisms from the core into the effluent. The first results of spatially and phase-resolved OES measurements of the discharge dynamics of the core are presented.

Is the flow tube reactor with NO2 titration a reliable absolute source for atomic hydrogen?

The H+NO2 titration scheme for the determination of atomic hydrogen densities within a microwave excited flow tube reactor has been investigated by laser-induced fluorescence spectroscopy in the vacuum UV. Absolute hydrogen densities are determined on the basis of calibration by Rayleigh scattering from argon. The measurement is performed at a gas mixture containing 0.5% of D2 added to the main gas H2. The ground state density of the hydrogen atoms generated in the flow tube reactor was inferred from the fluorescence radiation of the spectrally shifted optically thin D-Lyman-a transition.

Absolute Atomic Oxygen Density Distributions in the Effluent of a Micro Scale Atmospheric Pressure Plasma Jet

The coplanar microscale atmospheric pressure plasma jet (µ-APPJ) is a capacitively coupled radio frequency discharge (13.56 MHz, ~15W rf power) designed for optimized optical diagnostic access. It is operated in a homogeneous glow mode with a noble gas flow (1.4 slm He) containing a small admixture of molecular oxygen (~0.5%). Ground state atomic oxygen densities in the effluent up to 2 × 1014 cm-3 are measured by two-photon absorption laser-induced fluorescence spectroscopy (TALIF) providing space resolved density maps. The quantitative calibration of the TALIF setup is performed by comparative measurements with xenon. A maximum of the atomic oxygen density is observed for 0.6% molecular oxygen admixture. Furthermore, an increase in the rf power up to about 15W (depending on gas flow and mixture) leads to an increase in the effluent’s atomic oxygen density, then reaching a constant level for higher powers.

Absolute atomic oxygen density profiles in the discharge core of a microscale atmospheric pressure plasma jet

The micro atmospheric pressure plasma jet is an rf driven (13.56 MHz, ~20 W) capacitively coupled discharge producing a homogeneous plasma at ambient pressure when fed with a gas flow of helium (1.4 slm) containing small admixtures of oxygen (~0.5%). The design provides excellent optical access to the plasma core. Ground state atomic oxygen densities up to 3x1016 cm-3 are measured spatially resolved in the discharge core by absolutely calibrated two-photon absorption laser-induced fluorescence spectroscopy. The atomic oxygen density builds up over the first 8 mm of the discharge channel before saturating at a maximum level. The absolute value increases linearly with applied power.

Generation of Atomic Oxygen in the Effluent of an Atmospheric Pressure Plasma Jet

The planar 13.56MHz RF-excited low temperature atmospheric pressure plasma jet (APPJ) investigated in this study is operated with helium feed gas and a small molecular oxygen admixture. The effluent leaving the discharge through the jet’s nozzle contains very few charged particles and a high reactive oxygen species’ density. As its main reactive radical, essential for numerous applications, the ground state atomic oxygen density in the APPJ’s effluent is measured spatially resolved with two-photon absorption laser induced fluorescence spectroscopy. The atomic oxygen density at the nozzle reaches a value of ~1016 cm-3. Even at several centimetres distance still 1% of this initial atomic oxygen density can be detected. Optical emission spectroscopy (OES) reveals the presence of short living excited oxygen atoms up to 10 cm distance from the jet’s nozzle. The measured high ground state atomic oxygen density and the unaccounted for presence of excited atomic oxygen require further investigations on a possible energy transfer from the APPJ’s discharge region into the effluent: energetic vacuum ultraviolet radiation, measured by OES down to 110 nm, reaches far into the effluent where it is presumed to be responsible for the generation of atomic oxygen.

The dynamics of radio-frequency driven atmospheric pressure plasma jets

The complex dynamics of radio-frequency driven atmospheric pressure plasma jets is investigated using various optical diagnostic techniques and numerical simulations. Absolute number densities of ground state atomic oxygen radicals in the plasma effluent are measured by two-photon absorption laser induced fluorescence spectroscopy (TALIF). Spatial profiles are compared with (vacuum) ultra-violet radiation from excited states of atomic oxygen and molecular oxygen, respectively. The excitation and ionization dynamics in the plasma core are dominated by electron impact and observed by space and phase resolved optical emission spectroscopy (PROES). The electron dynamics is governed through the motion of the plasma boundary sheaths in front of the electrodes as illustrated in numerical simulations using a hybrid code based on fluid equations and kinetic treatment of electrons.

New catanionic surfactants based on 1-alkyl-3-methylimidazolium alkylsulfonates, [C(n)H(2n+1)mim][CmH2m+1SO3]: mesomorphism and aggregation

Anionic and cationic alkyl-chain effects on the self-aggregation of both neat and aqueous solutions of 1-alkyl-3-methylimidazolium alkylsulfonate salts ([C(n)H(2n+ 1)mim][CmH2m+1SO3]; n = 8, 10 or 12; m = 1 and n = 4 or 8; m = 4 or 8) have been investigated. Some of these salts constitute a novel family of pure catanionic surfactants in aqueous solution. Examples of this class of materials are rare; they are distinct from both mixed cationic-anionic surfactants (obtained by mixing two salts) and gemini surfactants (with two or more amphiphilic groups bound by a covalent linker). Fluorescence spectroscopy and interfacial tension measurements have been used to determine critical micelle concentrations (CMCs), surface activity, and to compare the effects of the alkyl-substitution patterns in both the cation and anion on the surfactant properties of these salts. With relatively small methylsulfonate anions (n = 8, 10 and 12, m = 1), the salts behave as conventional single chain cationic surfactants, showing a decrease of the CMC upon increase of the alkyl chain length (n) in the cation. When the amphiphilic character is present in both the cation and anion (n = 4 and 8, m = 4 and 8), novel catanionic surfactants with CMC values lower than those of the corresponding cationic analogues, and which exhibited an unanticipated enhanced reduction of surface tension, were obtained. In addition, the thermotropic phase behaviour of [C(8)H(18)mim][C8H18SO3] (n = m = 8) was investigated using variable temperature X-ray scattering, polarising optical microscopy and differential scanning calorimetry; formation of a smectic liquid crystalline phase with a broad temperature range was observed.

Ionic liquid salt-induced inactivation and unfolding of cellulase from Trichoderma reesei

The potential for performing cellulase-catalyzed reactions on cellulose dissolved in 1-butyl-3-methylimidazolium chloride ([bmim] Cl) has been investigated. We have carried out a systematic study on the irreversible solvent and ionic strength-induced inactivation and unfolding of cellulase from Trichoderma reesei ( E.C.#3.2.1.4). Experiments, varying both cellulase and IL solvent concentrations, have indicated that [bmim] Cl, and several other ILs, as well as dimethylacetamide-LiCl (a well-known solvent system for cellulose), inactivate cellulase under these conditions. Despite cellulase inactivity, results obtained from this study led to valuable insights into the requirements necessary for enzyme activity in IL systems. Enzyme stability was determined during urea, NaCl, and [bmim] Cl-induced denaturation observed through fluorescence spectroscopy. Protein stability of a PEG-supported cellulase in [bmim] Cl solution was investigated and increased stability/activity of the PEG-supported cellulase in both the [bmim] Cl and citrate buffer solutions were detected.

Diagnostic-based modeling on a micro-scale atmospheric-pressure plasma jet

Diagnostic-based modeling (DBM) actively combines complementary advantages of numerical plasma simulations and relatively simple optical emission spectroscopy (OES). DBM is applied to determine spatial absolute atomic oxygen ground-state density profiles in a micro atmospheric-pressure plasma jet operated in He–O2. A 1D fluid model with semi-kinetic treatment of the electrons yields detailed information on the electron dynamics and the corresponding spatio-temporal electron energy distribution function. Benchmarking this time- and space-resolved simulation with phase-resolved OES (PROES) allows subsequent derivation of effective excitation rates as the basis for DBM. The population dynamics of the upper O(3p3P) oxygen state (? = 844 nm) is governed by direct electron impact excitation, dissociative excitation, radiation losses, and collisional induced quenching. Absolute values for atomic oxygen densities are obtained through tracer comparison with the upper Ar(2p1) state (? = 750.4 nm). The resulting spatial profile for the absolute atomic oxygen density shows an excellent quantitative agreement to a density profile obtained by two-photon absorption laser-induced fluorescence spectroscopy.