High sensitivity gas spectroscopy of porous, highly scattering solids

We present minimalistic and cost-efficient instrumentation employing tunable diode laser gas spectroscopy for the characterization of porous and highly scattering solids. The sensitivity reaches 3 x 10(-6) (absorption fraction), and the improvement with respect to previous work in this field is a factor of 10. We also provide the first characterization of the interference phenomenon encountered in high-resolution spectroscopy of turbid samples. Revealing that severe optical interference originates from the samples, we discuss important implications for system design. In addition, we introduce tracking coils and sample rotation as new and efficient tools for interference suppression. The great value of the approach is illustrated in an application addressing structural properties of pharmaceutical materials.     

Application of multivariate analysis of TOF-SIMS spectra for studying the effect of high glucose intake on aortic lipid profile

Aim

To study the effect of long-term glucose feeding on aortic lipid composition by using the time of flight-secondary ion mass spectrometry (TOF-SIMS).

Method

Rats were divided into two groups, drinking water with or without 10% glucose from birth to 6 months of age. The aortic wall was dissected out, high-pressure frozen, freeze-fractured, freeze-dried and analyzed by TOF-SIMS using a Bismuth cluster ion source. Surface spectra were taken from standardized regions of the vessel wall.

Results

Different peaks, such as cholesterol, fatty acids (FAs) and diacylglycerols (DAGs), were identified by the principal component analysis as carries of variance between two groups. These peaks were then compared by conventional t-test. Our data showed that the intensity of cholesterol, but not FAs and DAGs, was significantly decreased in the glucose-drinking rat. Moreover, the long-term glucose intake changed ratios between different FAs in the aorta.

Conclusion

The long-term glucose intake led to decreased cholesterol intensity in the aortic wall and this effect was revealed through a global analytical approach with objective selection of significant variables.     

An α/β-HSQC-α/β Experiment for Spin-State Selective Editing of IS Cross Peaks

A generalized version of the TROSY experiment allows the spin-state selective editing of the four multiplet components of¹⁵N–¹H cross peaks of amide groups in proteins into four different subspectra, with no penalty in sensitivity. An improvement by in sensitivity results, if only two of the four multiplet components are selected. Use of the experiment for the measurement of¹J_HNcoupling constants is discussed. A water flip-back version of the experiment is demonstrated with a 45 kDa fragment of¹⁵N/²H labeledStaphylococcus aureusgyrase B.     

A method to determine dynamic loads on spur gear teeth and on bearings

A method is described which can be used to calculate dynamic gear tooth force and bearing forces. The model includes elastic bearings. The gear mesh stiffness and the path of contact are determined using the deformations of the gears and the bearings. This gives contact outside the plane-of-action and a time-varying working pressure angle. In a numerical example it is found that the only important vibration mode for the gear contact is the one where the gear tooth deformation is dominant. The bearing force variation, however, will be much more affected by the other vibration modes. The influence of the friction force is also studied. The friction has no dynamic influence on the gear contact force or on the bearing force in the gear mesh line-of-action direction. On the other hand, the changing of sliding directions in the pitch point is a source for critical oscillations of the bearings in the gear tooth frictional direction. These bearing force oscillations in the frictional direction appear unaffected by the dynamic response along the gear mesh line-of-action direction.     

Numerical simulation and laser-based imaging of mixture formation, ignition, and soot formation in a diesel spray

Laser-based imaging of fuel vapor distribution, ignition, and soot formation in diesel sprays was carried out in a high-pressure, high-temperature spray chamber under conditions that correspond to temperature and pressure in a diesel engine. Rayleigh scattering and laser-induced incandescence are used to image fuel density and soot volume fraction. The experimental results provide data for comparison with numerical simulations. An interactive cross-sectionally averaged spray model based on Eulerian transport equations was used for the simulation of the spray, and the turbulence-chemistry interaction was modeled with the representative interactive flamelet (RIF) concept. The flamelet calculation is coupled to the Kiva3V computational fluid dynamics (CFD) code using the scalar dissipation rate and pressure as an input to the RIF-code. The flamelet code computes the instationary flamelet profiles for every time step. These profiles were integrated over mixture fraction space using a prescribed β-PDF to obtain mean values, which are passed back to the CFD-code. Thereby, the temperature and the relevant species in each CFD-cell were obtained. The fuel distribution, the average ignition delay as well as the location of ignition are well predicted by the simulation. Furthermore, simulations show that the experimentally observed injection-to-injection variations in ignition delay are due to temperature inhomogeneities. Experimental and simulated spatial soot and fuel vapor density distributions are compared during and after second stage ignition.     

Rotational CARS N2 thermometry: validation experiments for the influence of nitrogen spectral line broadening by hydrogen

Rotational coherent anti‐Stokes Raman spectroscopy (CARS) in fuel‐rich hydrocarbon flames, with a large content of hydrogen in the product gases (∼20%), has in previous work shown that evaluated temperatures are raised several tens of Kelvin by taking newly derived N₂ H₂ Raman line widths into account. To validate these results, in this work calibrated temperature measurements at around 300, 500 and 700 K were performed in a cell with binary gas mixtures of nitrogen and hydrogen. The temperature evaluation was made with respect to Raman line widths either from self‐broadened nitrogen only, N₂ N₂ [energy‐corrected‐sudden (ECS)], or by also taking nitrogen broadened by hydrogen, N₂ H₂ [Robert–Bonamy (RB)], Raman line widths into account. With increased amount of hydrogen in the cell at constant temperature, the evaluated CARS temperatures were clearly lowered with the use of Raman line widths from self‐broadened nitrogen only, and the case with inclusion of N₂ H₂ Raman line widths was more successful. The difference in evaluated temperatures between the two different sets increases approximately linearly, reaching 20 K (at T ∼ 300 K), 43 K (at T = 500 K) and 61 K (at T = 700 K) at the highest hydrogen concentration (90%). The results from this work further emphasize the importance of using adequate Raman line widths for accurate rotational CARS thermometry. Copyright © 2010 John Wiley & Sons, Ltd.     

Efficient sample pre-concentration of bupivacaine from human plasma by solid-phase extraction on molecularly imprinted polymers

The ability to use imprinted polymers for solid-phase extraction is demonstrated in a model pre-concentration of bupivacaine from human plasma samples prior to gas chromatography. Imprinting of the structural analogue pentycaine yielded a sorbent which efficiently extracted analyte and internal standard, while possible interference on analyte quantification from leakage of remaining template molecules was eliminated. Human plasma samples were diluted with citrate buffer pH 5, and applied onto solid phase extraction columns containing 15 mg of imprinted sorbent. Wash steps with 20% methanol in water followed by acetonitrile preceded elution with 2% triethylamine in acetonitrile. A direct comparison with conventional sample pre-treatment methods showed the high selectivity of the imprinted sorbent resulted in distinctly cleaner chromatographic traces than were obtained both after liquid-liquid extraction and C18-based solid-phase extraction.     

Carboxyl groups in pre-treated regenerated cellulose fibres

The influence of peroxide bleaching and slack-mercerization on the amount of acidic groups in regenerated fibres (viscose, modal and lyocell) were studied. Conductometric titration was used to determine the total content of acidic carboxylic groups. Polyelectrolyte titration was used for surface and total charge determination, and to obtain information about the charge distribution and accessibilities of charged groups. Changes in fibre crystallinity to pre-treatment processes were characterized using iodine sorption (Schwertassek method) and correlated to treatments and the amount of carboxylic groups. For all three types of fibres the amount of accessible carboxyl groups was lowered by an increase in the degree of crystallinity. Bleaching with hydrogen peroxide causes some oxidative cellulose damage and, therefore, a larger amount of carboxyl groups (presumably formed at the end of cellulose chains). Slack-mercerization did not significantly change the total amount of acidic groups in the fibres, but their accessibility to cationic polyelectrolytes, in particular to polymers with high molecular weight was substantially lowered. Lidija Fras Zemljič, Zdenka Peršin, and Karin Stana Kleinschek are the members of the European Polysaccharide Network of Excellence (EPNOE).     

Quantum Monte Carlo calculations of the potential energy curve of the helium dimer

We report results of two quantum Monte Carlo methods -- variational Monte Carlo and diffusion Monte Carlo -- on the potential energy curve of the helium dimer. In contrast to previous quantum Monte Carlo calculations on this system, we have employed trial wave functions of the Slater-Jastrow form and used the fixed node approximation for the fermion nodal surface. We find both methods to be in excellent agreement with the best theoretical results at short range. In addition, the diffusion Monte Carlo results give very good agreement across the whole potential energy curve, while the Slater-Jastrow wave function fails to bind the dimer at all.