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.     

Origin and Processing Methods Slightly Affect Allergenic Characteristics of Cashew Nuts (Anacardium occidentale)

The protein content and allergen composition was studied of cashews from 8 different origins (Benin, Brazil, Ghana, India, Ivory Coast, Mozambique, Tanzania, Vietnam), subjected to different in‐shell heat treatments (steamed, fried, drum‐roasted). On 2D electrophoresis, 9 isoforms of Ana o 1, 29 isoforms of Ana o 2 (11 of the acidic subunit, 18 of the basic subunit), and 8 isoforms of the large subunit of Ana o 3 were tentatively identified. Based on 1D and 2D electrophoresis, no difference in allergen content (Ana o 1, 2, 3) was detected between the cashews of different origins (P > 0.5), some small but significant differences were detected in allergen solubility between differently heated cashews. No major differences in N‐ and C‐terminal microheterogeneity of Ana o 3 were detected between cashews of different origins. Between the different heat treatments, no difference was detected in glycation, pepsin digestibility, or IgE binding of the cashew proteins.     

High-spatial resolution mass spectrometric imaging of peptide and protein distributions on a surface

For the first time macromolecular ion microscope images have been recorded using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Single-shot, mass-resolved images of the spatial distributions of intact peptide and protein ions over an area of 200 microm in diameter were obtained in less than 1 ms at a repetition rate of 12 Hz. The magnifying ion optics of the ion microscope allowed ion images to be obtained with a lateral resolution of 4 microm. These results prove the concept of high-resolution MALDI-MS imaging in microscope mode without the need for a tight laser focus and the accompanying sensitivity losses. The ion microscopy approach offers an improvement of several orders of magnitude in speed of acquisition compared to the conventional (microprobe) approach to MALDI-MS imaging.     

Using matrix peaks to map topography: increased mass resolution and enhanced sensitivity in chemical imaging

It is well known in secondary ion mass spectrometry (SIMS) that sample topography leads to decreased mass resolution. Specifically, the ion's time of flight is dependent on where it was generated. Here, using matrix-enhanced SIMS, it is demonstrated that, in addition to increasing the yield of intact pseudomolecular ions, the matrix allows the user to semiquantitatively record the topography of a sample. Through mapping the topography-related mass shifts of the matrix (which leads to decreased mass resolution), the analogous mass shifts of higher mass ions can be deconvoluted and higher resolution and greater sensitivity obtained. Furthermore, the semiquantitative topographical map obtained can be compared with any chemical images obtained, allowing the user to quickly ascertain whether local intensity maximums are due to topological features or represent genuine features of interest.     

The Sensitivity Matrix: Using Advanced Auditory Models in Speech and Audio Processing

Perceptually optimal processing of speech and audio signals demands a rigorous approach using a distortion measure that resembles human perception. This requires distortion measures based on sophisticated, complex auditory models. Under the assumption of small distortions these models can be simplified by means of a sensitivity matrix. In this paper, we show the power of this approach. We present a method to derive the sensitivity matrix for distortion measures based on spectro-temporal auditory models. This method is applied to an example auditory model and the region of validity of the approximation and the application of linear algebra to analyze the characteristics of the given model are discussed. Furthermore, we show how to build a coder minimizing a sensitivity matrix distortion measure given the typically long support of a perceptual distortion measure     

HMM-Based Gain Modeling for Enhancement of Speech in Noise

Accurate modeling and estimation of speech and noise gains facilitate good performance of speech enhancement methods using data-driven prior models. In this paper, we propose a hidden Markov model (HMM)-based speech enhancement method using explicit gain modeling. Through the introduction of stochastic gain variables, energy variation in both speech and noise is explicitly modeled in a unified framework. The speech gain models the energy variations of the speech phones, typically due to differences in pronunciation and/or different vocalizations of individual speakers. The noise gain helps to improve the tracking of the time-varying energy of nonstationary noise. The expectation-maximization (EM) algorithm is used to perform offline estimation of the time-invariant model parameters. The time-varying model parameters are estimated online using the recursive EM algorithm. The proposed gain modeling techniques are applied to a novel Bayesian speech estimator, and the performance of the proposed enhancement method is evaluated through objective and subjective tests. The experimental results confirm the advantage of explicit gain modeling, particularly for nonstationary noise sources     

Comparative emission analysis of low-energy and zero-emission buildings

Different designs and concepts of low-energy and zero-emission buildings (ZEBs) are being introduced into the Norwegian market. This study analyses and compares the life cycle emissions of CO₂ equivalents (CO₂e) from eight different single-family houses in the Oslo climate. Included are four ZEBs: one active house, two passive houses, and a reference house (Norwegian building code of 2010). Monthly differences in CO₂e emissions are calculated for the seasonally sensitive Norwegian context for electricity generation and consumption. This is used to supplant the previous applied symmetric weighting approach for CO₂e/kWh factors for import and export of electricity for the ZEB cases. All the ZEBs have lower use-stage emissions compared with the other buildings or the reference case. Embodied impacts are found to be 60–75% for the analysed ZEB cases, confirming the importance of embodied impacts in Norwegian ZEBs. The lowest total emissions were from the smallest ZEB, emphasizing area efficiency. The highest emissions were from the reference case. By abandoning the symmetric approach, a new perspective was developed for assessing the performance of ZEBs within the Norwegian context. One of four ZEB cases managed to balance out its annual energy-related emissions.     

An assessment view to evaluate whether Spatial Data Infrastructures meet their goals

The motives for constructing Spatial Data Infrastructures (SDIs) are often based on their anticipated benefits for society, economy, and environment. According to those widely articulated but rarely proven benefits, SDI coordinators have been defining more specific objectives to be achieved by their SDIs. However, there is a limited number of assessment approaches that are able to demonstrate whether SDIs indeed realize the intended goals. In this article we develop, apply and evaluate an assessment view for evaluating the extent to which SDIs realize their goals. The assessment view has been developed stepwise using the Multi-view SDI assessment framework as a guideline. The application of the proposed view in the Dutch SDI demonstrates its potential. In addition, the evaluation of the proposed view by the potential users confirms to a certain extent its usability. The results also show that the ease of determining assessment indicators depends on the precision with which the SDI goals are formulated.     

Capillary electrophoresis in clinical and forensic analysis

During the past decade, capillary electrophoresis (CE) emerged as a promising, effective and economic approach for separation of a large variety of substances, including those encountered in clinical and forensic analysis. Reliable and automated CE instruments became commercially available and promoted the exploration of an increasing number of CE methods and fields of application. The widespread applicability of CE, its enormous separation power and high-sensitivity detection schemes make this technology an attractive and promising tool. This review discusses the principles and important aspects of CE-based assays and provides an overview of the key achievements encountered with CE in clinical and forensic analysis, including those associated with the analysis of serum proteins, hemoglobin variants, drugs and nucleic acids. Validated assays, interesting applications and future trends in clinical and forensic analysis are also discussed.     

Gold-enhanced biomolecular surface imaging of cells and tissue by SIMS and MALDI mass spectrometry

Surface metallization by plasma coating enhances desorption/ionization of membrane components such as lipids and sterols in imaging time-of-flight secondary ion mass spectrometry (TOF-SIMS) of tissues and cells. High-resolution images of cholesterol and other membrane components were obtained for neuroblastoma cells and revealed subcellular details (resolving power 1.5 mum). Alternatively, in matrix-enhanced SIMS, 2,5-dihydroxybenzoic acid electrosprayed on neuroblastoma cells allowed intact molecular ion imaging of phosphatidylcholine and sphingomyelin at the cellular level. Gold deposition on top of matrix-coated rat brain tissue sections strongly enhanced image quality and signal intensity in stigmatic matrix-assisted laser desorption/ionization imaging mass spectrometry. High-quality total ion count images were acquired, and the neuropeptide vasopressin was localized in the rat brain tissue section at the hypothalamic area around the third ventricle. Although the mechanism of signal enhancement by gold deposition is under debate, the results we have obtained for cells and tissue sections illustrate the potential of this sample preparation technique for biomolecular surface imaging by mass spectrometry.