Revisiting spontaneous Raman scattering for direct oxygen atom quantification.

In this Letter, the counterintuitive and largely unknown Raman activity of oxygen atoms is evaluated for its capacity to determine absolute densities in gases with significant O-density. The study involves ${\rm CO}_2$ microwave plasma to generate a self-calibrating mixture and establish accurate cross sections for the $^3{\!P_2}{\leftrightarrow ^3}{\!P_1}$ and $^3{\!P_2}{\leftrightarrow ^3}{\!P_0}$ transitions. The approach requires conservation of stoichiometry, confirmed within experimental uncertainty by a 1D fluid model. The measurements yield ${\sigma _{J = 2 \to 1}} = 5.27 \pm _{{\rm sys}:0.53}^{{\rm rand}:0.17} \times {10^{- 31}}\;{{\rm cm}^2}/{\rm sr}$ and ${\sigma _{J = 2 \to 0}} = 2.11 \pm _{{\rm sys}:0.21}^{{\rm rand}:0.06} \times {10^{- 31}}\;{{\rm cm}^2}/{\rm sr}$, and the detection limit is estimated to be $1 \times {10^{15}}\;{{\rm cm}^{- 3}}$ for systems without other scattering species.

How the alternating degeneracy in rotational Raman spectra of CO2 and C2H2 reveals the vibrational temperature.

The contribution of higher vibrational levels to the rotational spectrum of linear polyatomic molecules with a center of symmetry (CO2 and C2H2) is assessed. An apparent nuclear degeneracy is analytically formulated by vibrational averaging and compared to numerical averaging over vibrational levels. It enables inferring the vibrational temperature of the bending and asymmetric stretching modes from the ratio of even to odd peaks in the rotational Raman spectrum. The contribution from higher vibrational levels is already observable at room temperature as g˜e/o=0.96/0.04 for CO2 and g˜e/o=1.16/2.84 for C2H2. The use of the apparent degeneracy to account for higher vibrational levels is demonstrated on spectra measured for a CO2 microwave plasma in the temperature range of 300-3500 K, and shown to be valid up to 1500 K.

Taming microwave plasma to beat thermodynamics in CO2 dissociation.

The strong non-equilibrium conditions provided by the plasma phase offer the opportunity to beat traditional thermal process energy efficiencies via preferential excitation of molecular vibrations. Simple molecular physics considerations are presented to explain potential dissociation pathways in plasma and their effect on energy efficiency. A common microwave reactor approach is evaluated experimentally with Rayleigh scattering and Fourier transform infrared spectroscopy to assess gas temperatures (exceeding 10(4) K) and conversion degrees (up to 30%), respectively. The results are interpreted on a basis of estimates of the plasma dynamics obtained with electron energy distribution functions calculated with a Boltzmann solver. It indicates that the intrinsic electron energies are higher than is favorable for preferential vibrational excitation due to dissociative excitation, which causes thermodynamic equilibrium chemistry to dominate. The highest observed energy efficiencies of 45% indicate that non-equilibrium dynamics had been at play. A novel approach involving additives of low ionization potential to tailor the electron energies to the vibrational excitation regime is proposed.

The Chemical Origins of Plasma Contraction and Thermalization in CO2 Microwave Discharges.

Thermalization of electron and gas temperature in CO2 microwave plasma is unveiled with the first Thomson scattering measurements. The results contradict the prevalent picture of an increasing electron temperature that causes discharge contraction. It is known that as pressure increases, the radial extension of the plasma reduces from ∼7 mm diameter at 100 mbar to ∼2 mm at 400 mbar. We find that, simultaneously, the initial nonequilibrium between ∼2 eV electron and ∼0.5 eV gas temperature reduces until thermalization occurs at 0.6 eV. 1D fluid modeling, with excellent agreement with measurements, demonstrates that associative ionization of radicals, a mechanism previously proposed for air plasma, causes the thermalization. In effect, heavy particle and heat transport and thermal chemistry govern electron dynamics, a conclusion that provides a basis for ab initio prediction of power concentration in plasma reactors.

Rotation of a strongly magnetized hydrogen plasma column determined from an asymmetric Balmer-beta spectral line with two radiating distributions.

A potential buildup in front of a magnetized cascaded arc hydrogen plasma source is explored via E x B rotation and plate potential measurements. Plasma rotation approaches thermal speeds with maximum velocities of 10 km/s. The diagnostic for plasma rotation is optical emission spectroscopy on the Balmer-beta line. Asymmetric spectra are observed. A detailed consideration is given on the interpretation of such spectra with a two distribution model. This consideration includes radial dependence of emission determined by Abel inversion of the lateral intensity profile. Spectrum analysis is performed considering Doppler shift, Doppler broadening, Stark broadening, and Stark splitting.

High sensitivity imaging Thomson scattering for low temperature plasma.

A highly sensitive imaging Thomson scattering system was developed for low temperature (0.1-10 eV) plasma applications at the Pilot-PSI linear plasma generator. The essential parts of the diagnostic are a neodymium doped yttrium aluminum garnet laser operating at the second harmonic (532 nm), a laser beam line with a unique stray light suppression system and a detection branch consisting of a Littrow spectrometer equipped with an efficient detector based on a "Generation III" image intensifier combined with an intensified charged coupled device camera. The system is capable of measuring electron density and temperature profiles of a plasma column of 30 mm in diameter with a spatial resolution of 0.6 mm and an observational error of 3% in the electron density (n(e)) and 6% in the electron temperature (T(e)) at n(e) = 4 x 10(19) m(-3). This is achievable at an accumulated laser input energy of 11 J (from 30 laser pulses at 10 Hz repetition frequency). The stray light contribution is below 9 x 10(17) m(-3) in electron density equivalents by the application of a unique stray light suppression system. The amount of laser energy that is required for a n(e) and T(e) measurement is 7 x 10(20)n(e) J, which means that single shot measurements are possible for n(e)>2 x 10(21) m(-3).

High resolution end group determination of low molecular weight polymers by matrix-assisted laser desorption ionization on an external ion source fourier transform ion cyclotron resonance mass spectrometer.

Matrix-assisted laser desorption ionization was performed on an external ion source Fourier transform ion cyclotron resonance mass spectrometer equipped with a 7-T superconducting magnet to analyze end groups of synthetic polymers in the mass range from 500 to 5000 u. Native, perdeutero methylated, propylated, and acetylated polyethylene glycol and polyvinyl pyrrolidone with unknown end-group elemental composition were investigated in the mass range up to 5000 u by using a 2,5-dihydroxybenzoic acid matrix. A small electrospray setup was used for the deposition of the samples. Two methods to process data were evaluated for the determination of end groups from the measured masses of the component molecules in the molecular weight ranges: a regression method and an averaging method. The averaging method is demonstrated to allow end-group mass determinations with an accuracy within 3 mu for the molecular weight range from 500 to 1400 and within 20 mu for the molecular weight range from 3400 to 5000. This is sufficient to identify the elemental composition of end groups in unknown polymer samples.

Diagnosing ions and neutrals via n=2 excited hydrogen atoms in plasmas with high electron density and low electron temperature.

Ion and neutral parameters are determined in the high electron density, magnetized, hydrogen plasma beam of an ITER divertor relevant plasma via measurements of the n=2 excited neutrals. Ion rotation velocity (up to 7 km/s) and temperature (2-3 eV~T_{e}) are obtained from analysis of Hα spectra measured close to the plasma source. The methodology for neutral density determination is explained whereby measurements in the linear plasma beam of Pilot-PSI are compared to modeling. Ground-state atomic densities are obtained via the production rate of n=2 and the optical thickness of the Lyman-α transition (escape factor ~0.6) and yield an ionization degree >85% and dissociation degree in the residual gas of ~4%. A 30% proportion of molecules with a rovibrational excitation of more than 2 eV is deduced from the production rate of n=2 atoms. This proportion increases by more than a factor of 4 for a doubling of the electron density in the transition to ITER divertor relevant electron densities, probably because of a large increase in the production and confinement of ground-state neutrals. Measurements are made using laser-induced fluorescence (LIF) and absorption, the suitability of which are evaluated as diagnostics for this plasma regime. Absorption is found to have a much better sensitivity than LIF, mainly owing to competition with background emission.

Image calibration in fluorescence microscopy.

A fluorescence image calibration method is presented based on the use of standardized uniformly fluorescing reference layers. It is demonstrated to be effective for the correction of non-uniform imaging characteristics across the image (shading correction) as well as for relating fluorescence intensities between images taken with different microscopes or imaging conditions. The variation of the illumination intensity over the image can be determined on the basis of the uniform bleaching characteristics of the layers. This permits correction for the latter and makes bleach-rate-related imaging practical. The significant potential of these layers for calibration in quantitative fluorescence microscopy is illustrated with a series of applications. As the illumination and imaging properties of a microscope can be evaluated separately, the methods presented are also valuable for general microscope testing and characterization.

Endgroup analysis of polyethylene glycol polymers by matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectrometry.

Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS) by external injection of matrix-assisted laser desorbed and ionized (MALDI) polymers offers good possibilities for characterization of low molecular weight homopolymers (MW range up to 10 kDa). The molecular masses of the molecular weight distribution (MWD) components of underivatized and derivatized (dimethyl, dipropyl, dibutyl and diacetyl) polyethylene glycol (PEG) 1000 and 4000 were measured by MALDI-FTICR-MS. These measurements have been performed using a commercial FTICR spectrometer with a home-built external ion source. MALDI of the samples with a 2,5-dihydroxybenzoic acid matrix in a 1000:1 matrix-to-analyte molar ratio produces sodiated molecules in a sufficient yield to trap the ions in the ICR cell. The masses of the molecular weight distribution of PEG components were measured in broad-band mode with a mass accuracy of < 5 ppm in the mass range around 1000 u and within 40 ppm accuracy around 4000 u. From these measurements, the endgroup mass of the polymer was determined by correlation of the measured component mass with the degree of polymerization. The masses of the PEG endgroups have been determined within a deviation of 3-10 millimass units for the PEG1000 derivatives and 10-100 millimass units for the PEG4000 derivatives, thus confirming the identity of the distal parts of the model compounds.

Determination of Block Length Distributions of Poly(oxypropylene) and Poly(oxyethylene) Block Copolymers by MALDI-FTICR Mass Spectrometry.

Matrix-assisted laser desorption/ionization (MALDI) was performed on an external ion source Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS) to analyze the block length distributions of triblock polymers of poly(oxypropylene) and poly(oxyethylene). The first series of results presented demonstrate that the apparent molecular weight distributions are distorted. This distortion is induced by the flight-time-induced mass discrimination inherent in the experimental technique, the variation of isotopic patterns over the measured mass range, and the overlap of peaks in the spectrum. Subsequently, a method for the treatment of molecular weight distributions measured by MALDI on an external ion source FTICR-MS is developed to yield the actual molecular weight distribution and, from that, the individual block length distributions. For the first time, detailed and accurate molecular weight data were obtained on a complex sample using this methodology, which independently validates the data provided by the manufacturer. The experimentally verified random coupling hypothesis proves the validity of the methodology.

LDL oxidative modifications in well- or moderately controlled type 2 diabetes.

BACKGROUND: The aim of the study was to examine, by measurement of specific indicators of free radical-mediated oxidation of LDL, whether there is evidence of increased in vivo oxidation of LDL in type 2 diabetic patients, and to investigate their associations with carotid intima media thickness (IMT). METHODS: In native LDL, we quantified five different products of LDL oxidation reflecting various stages of LDL oxidative modification in 38 individuals with well- or moderately controlled type 2 diabetes (HbA(1c)