Cryogenic probe 13C NMR spectroscopy of urine for metabonomic studies

Cryogenic probe technology can significantly compensate for the inherently low sensitivity of natural abundance 13C NMR spectroscopy. This now permits its routine use in NMR spectroscopy of biofluids, such as urine or plasma, with acquisition times that enable a high throughput of samples. Metabonomic studies often generate numerous samples in order to characterize fully the time-dependent biochemical response to stimuli, but until now, they have been largely conducted using 1H NMR spectroscopy because of its high sensitivity and hence efficient data acquisition. Here, we demonstrate that information-rich 13C NMR spectra of rat urine can be obtained using appropriately short acquisition times suitable for biochemical samples when using a cryogenic probe. Furthermore, these data were amenable to automated pattern recognition analysis, which produced a profile of the metabolic response to the model hepatotoxin hydrazine that was consistent with earlier studies. Thus, a new source of detailed and complementary information is available to metabonomics using cryogenic probe 13C NMR spectroscopy.     

Inversion with regularization for the retrieval of tropospheric aerosol parameters from multiwavelength lidar sounding

We present an inversion algorithm for the retrieval of particle size distribution parameters, i.e., mean (effective) radius, number, surface area, and volume concentration, and complex refractive index from multiwavelength lidar data. In contrast to the classical Tikhonov method, which accepts only that solution for which the discrepancy reaches its global minimum, in our algorithm we perform the averaging of solutions in the vicinity of this minimum. This averaging stabilizes the underlying ill-posed inverse problem, particularly with respect to the retrieval of number concentration. Results show that, for typical tropospheric particles and 10% error in the optical data, the mean radius could be retrieved to better than 20% from a lidar on the basis of a Nd:YAG laser, which provides a combination of backscatter coefficients at 355, 532, and 1064 nm and extinction coefficients at 355 and 532 nm. The accuracy is improved if the lidar is also equipped with a hydrogen Raman shifter. In this case two additional backscatter coefficients at 416 and 683 nm are available. The combination of two extinction coefficients and five backscatter coefficients then allows one to retrieve not only averaged aerosol parameters but also the size distribution function. There was acceptable agreement between physical particle properties obtained from the evaluation of multiwavelength lidar data taken during the Lindenberg Aerosol Characterization Experiment in 1998 (LACE 98) and in situ data, which were taken aboard aircraft.     

Ermittlung der Sequenzverteilung und Taktizität bei Acrylnitrill/Vinylidenchlorid-Copolymeren

An acrylonitrile/vinylidene chloride copolymer prepared by continuous suspension polymerization in aqueous medium was examined by carbon magnetic resonance at 90.52 MHz. The sequence distribution was evaluated from the diad and tetrad distribution of the methylene carbon regions and from the triad distributions of the other carbon atoms. The stereochemical configuration of the acrylonitrile units was determined from the peaks of the methine and the nitrile carbons which showed a low preference of the isotactic triad against the syndiotactic triad in agreement with freeradical polymerized polyacrylonitrile.     

Effect of peat decomposition and mass loss on historic mercury records in peat bogs from patagonia

Ombrotrophic peat bogs have been widely used to evaluate long-term records of atmospheric mercury (Hg) deposition. One of the major aims of these investigations is the estimation of the increase in atmospheric Hg fluxes during the industrial age compared to preindustrial fluxes. Comparability of Hg accumulation rates calculated from density, peat accumulation rates, and Hg concentrations requires linearity between these parameters. Peat formation is a dynamic process accompanied by intense mass loss and alteration of the organic material. Our investigations on three peat cores from the Magellanic Moorlands, Chile, indicate that Hg concentrations in peat strongly depend on peat humification. Moreover, differences in mass accumulation rates during peat evolution are not compensated by linear changes in density, peat accumulation, or Hg concentrations. We suggest that Hg accumulation rates be normalized to carbon accumulation rates to achieve comparability of Hg accumulation rates derived from differently altered peat sections. Normalization to the carbon accumulation rates reduces Hg accumulation rates in less degraded peat sections in the upper peat layers by factors of more than 2. Our results suggest that the increase in Hg deposition rates during modern times derived from ombrotrophic peat bogs are potentially overestimated if Hg accumulation rates are not corrected for mass accumulation rates.     

Production and physicochemical characterization of resistant starch type III derived from pea starch

Smooth pea starch was used for the production of physiological important resistant starch type III. For reduction of the molecular weight of the starch, different strategies including enzymatic debranching and acid hydrolysis (lintnerization), were tested to obtain an optimal starting material for retrogradation. The resulting polymer chain lengths were analyzed by high-performance anion-exchange chromatography. Temperature regimes and starch concentrations in gel were optimized during the retrogradation with the aim to obtain a high yield of resistant starch. Optimal conditions led to resistant starch contents up to 74%. The products were thermostable and showed no loss of resistant structures after autoclaving. The peak temperatures of the thermal transition were at approximately 147 degrees C. The resulting resistant starch products are suitable for the generation of functional foods.     

Effects of atmospheric ozone on microarray data quality

A data anomaly was observed that affected the uniformity and reproducibility of fluorescent signal across DNA microarrays. Results from experimental sets designed to identify potential causes (from microarray production to array scanning) indicated that the anomaly was linked to a batch process; further work allowed us to localize the effect to the posthybridization array stringency washes. Ozone levels were monitored and highly correlated with the batch effect. Controlled exposures of microarrays to ozone confirmed this factor as the root cause, and we present data that show susceptibility of a class of cyanine dyes (e.g., Cy5, Alexa 647) to ozone levels as low as 5-10 ppb for periods as short as 10-30 s. Other cyanine dyes (e.g., Cy3, Alexa 555) were not significantly affected until higher ozone levels (> 100 ppb). To address this environmental effect, laboratory ozone levels should be kept below 2 ppb (e.g., with filters in HVAC) to achieve high quality microarray data.     

Accounting for Lag Order Uncertainty in Autoregressions: the Endogenous Lag Order Bootstrap Algorithm

Conventional asymptotic and bootstrap methods for finite-order autoregressive models condition on the estimated lag order of the model as though it were known to be the true lag order. Even if the order is estimated correctly, this procedure ignores the sampling uncertainty about the lag order estimate and may result in spurious inferences. In this paper an appropriately modified bootstrap algorithm is introduced that reflects the true extent of sampling uncertainty in the regression estimates. This endogenous lag order bootstrap algorithm recognizes that lag order selection is an integral part of the sampling procedure by re-estimating the lag order in each bootstrap iteration. It is suggested that the endogenous lag order bootstrap algorithm should routinely replace the standard bootstrap algorithm in applications. Monte Carlo simulations show that ignoring lag order uncertainty may seriously undermine the coverage accuracy of bootstrap confidence intervals for vector autoregression impulse response estimates. Endogenizing the lag order choice is shown to improve coverage accuracy in small samples at negligible additional computational cost. As the lag order uncertainty declines in large samples, the performance of the endogenous lag order interval converges to that of the standard interval.     

Modelling oxygen diffusion and cell growth in a porous, vascularising scaffold for soft tissue engineering applications

Soft tissue engineering presents significant challenges compared to other tissue engineering disciplines such as bone, cartilage or skin engineering. The very high cell density in most soft tissues, often combined with large implant dimensions, means that the supply of oxygen is a critical factor in the success or failure of a soft tissue scaffold. A model is presented for oxygen diffusion in a 15-60 mm diameter dome-shaped scaffold fed by a blood vessel loop at its base. This model incorporates simple models for vascular growth, cell migration and the effect of cell density on the effective oxygen diffusivity. The model shows that the dynamic, homogeneous cell seeding method often employed in small-scale applications is not applicable in the case of larger scale scaffolds such as these. Instead, we propose the implantation of a small biopsy of tissue close to a blood supply within the scaffold as a technique more likely to be successful.     

Dimensioning of membrane bioreactors for municipal wastewater treatment.

A basic procedure is proposed for dimensioning membrane bioreactors that is generally applicable. It evaluates the required membrane surface with particular consideration of loading combinations and hydraulic loading characteristics; it also takes into account ranges of minimum temperatures and corresponding fluxes as given by suppliers. The procedures, while likely to require further improvement, should make MBR design more transparent and aid the comparison of design variants.