Structural classification of Quillaja saponins by electrospray ionization ion trap multiple-stage mass spectrometry in combination with multivariate analysis, proof of concept

MS² and MS³ spectra of thirteen previously identified saponin structures from Quillaja saponaria Molina were obtained by electrospray ionization ion trap multiple-stage mass spectrometry (ESI-ITMSⁿ) in positive ion mode. The spectra were analysed by partial least squares regression-discriminant analysis (PLS-DA) yielding a method that can classify the spectra according to saponin structure. For this method a referencing of the m/z axis was essential to obtain a correlation between peaks in the spectra and common structural elements. The MS² and MS³ spectra could be classified according to the structures of the oligosaccharides at C-3 and C-28 of the corresponding saponins. Terminal residues with the same mass, such as β-d-Apif and β-d-Xylp, could also be distinguished. The PLS-DA method was applied on Quillaja saponins separated from a commercial bark extract by reversed-phase chromatography.The method outlined here is applied on a specific group of Quillaja saponins, but can be used on other types of glycoconjugates. Combination of this technique with chromatography would give a very powerful tool for rapid identification of components in complex mixtures.     

Molecular mechanisms involved in creep phenomena of paper

The phenomenon of mechanosorptive creep (i.e., the increasing creep occurring in some hygroscopic materials subjected to moisture cycling) was studied for paper from a molecular point of view. Paper was tested in creep at different loading levels in a constant high humidity of 90% relative humidity (RH) and in a cyclic climate between 30 and 90% RH. Throughout the creep tests, spectra from the mid‐ and near‐IR, as well as dynamic mechanical data, were recorded to determine molecular changes occurring with time. In tensile stress scans the instantaneous, dynamic elastic modulus was found to increase. It is suggested that this increase was due to orientation of the cellulose molecules, which was detected as changes in the mid‐IR spectra at 1160 cm⁻¹ assigned to the C₁ O C₄ stretching. During creep in constant and cyclic humidity, the modulus was found to increase with time, more so for the cyclic humidity. Changes in the mid‐IR spectra at 1184 and 1030 cm⁻¹, which is assigned to CH₂, CH, and C O, may indicate sliding between the cellulose chains. The near‐IR measurements mainly showed differences in the moisture content. In stress scans the moisture content increased with increasing tensile load. In creep at constant 90% RH, the moisture content was also found to increase in a manner similar to the stress scan. In the cyclic humidity with a conditioning time of 70 min at 90% RH the moisture content decreased successively with increasing numbers of cycles. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1590–1595, 2001     

Performance analysis of general tracking algorithms

A general family of tracking algorithms for linear regression models is studied. It includes the familiar least mean square gradient approach, recursive least squares, and Kalman filter based estimators. The exact expressions for the quality of the obtained estimates are complicated. Approximate, and easy-to-use, expressions for the covariance matrix of the parameter tracking error are developed. These are applicable over the whole time interval, including the transient, and the approximation error can be explicitly calculated     

Issues in sampling and estimating continuous-time models with stochastic disturbances

The standard continuous time state space model with stochastic disturbances contains the mathematical abstraction of continuous time white noise. To work with well defined, discrete time observations, it is necessary to sample the model with care. The basic issues are well known, and have been discussed in the literature. However, the consequences have not quite penetrated the practice of estimation and identification. One example is that the standard model of an observation, being a snapshot of the current state plus noise independent of the state, cannot be reconciled with this picture. Another is that estimation and identification of time continuous models require a more careful treatment of the sampling formulas. We discuss and illustrate these issues in the current contribution. An application of particular practical importance is the estimation of models based on irregularly sampled observations.     

The influence of contact zone configuration on the flow structure in a dissolved air flotation pilot plant

The dissolved air flotation process is used in water and wastewater treatment. Among many parameters the fluid dynamics determine the capacity of the process. The contact zone is assumed to be important for the removal function, as it is believed to be the location for the aggregation of bubbles and flocs. This paper presents an experimental study on the flow structure in a contact zone of a DAF pilot tank and the influence of contact zone configuration. The flow structure in the contact zone was examined for different horizontal lengths of the zone and for different heights and inclinations of the shaft wall. The hydraulic surface loading was 11 m/h over the total tank surface area and the recycle rate was constant at 10% of the main flow. The examined hydraulic surface loading over the contact zone ranged from 40 to 98 m/h. Water velocities in the longitudinal, central section of the tank were measured with an acoustical Doppler velocimeter in a grid net for the different contact zone configurations, giving an insight into the flow structure. The result showed that the flow structure in the contact zone was characterised by a turbulent lower region and a plug-flow higher region. The hydraulic surface loading, a function of the length of the contact zone, seemingly determined the extension of the turbulent region. A higher hydraulic surface loading decreased the turbulent region while the lower loading increased it. A hydraulic surface loading of 65 m/h was suggested for design. It was not possible to determine the turbulent intensity quantitatively due to the measurement method. The height and inclination of the shaft wall did not seem to have a significant influence on the turbulent region. However, an increased height of the contact zone enhanced the higher, plug flow region and a recommended height of 0.81 m or higher for the recommended hydraulic surface loading was suggested when both mixing and plug-flow are desired. The separation zone was characterised by a stratified flow structure, mainly influenced by the cross-flow velocity that is a function of the distance between the shaft wall top and the water surface. A cross-flow velocity of 37m/h or higher resulted in a clearly defined stratification, believed to be crucial for an efficient separation of flocs. Finally, the extension of the lower, denser plug-flow region in the separation zone increased when the shaft wall height increased.     

Phase transitions and thermodynamic properties of dense assemblies of truncated nanocubes and cuboctahedra

Inspired by recent advances on the self-assembly of non-spherical nanoparticles, Monte Carlo simulations of the packing and thermodynamic properties of truncated nanocubes and cuboctahedra have been performed. The ergodicity problem was overcome by a modified Wang-Landau entropic sampling algorithm and equilibrium structural and thermodynamic properties were computed over a wide density range for both non-interacting and interacting particles. We found a structural transition from a simple cubic to a rhombohedral order when the degree of truncation exceeds a value of 0.9.     

Nanodevices: Location of Biomarkers and Reagents within Agarose Beads of a Programmable Nano‐bio‐chip (Small 5/2011)

The slow development of cost‐effective medical microdevices with strong analytical performance characteristics is due to a lack of selective and efficient analyte capture and signaling. The recently developed programmable nano‐bio‐chip (PNBC) is a flexible detection device with analytical behavior rivaling established macroscopic methods. The PNBC system employs ≈300 μm‐diameter bead sensors composed of agarose “nanonets” that populate a microelectromechanical support structure with integrated microfluidic elements. The beads are an efficient and selective protein‐capture medium suitable for the analysis of complex fluid samples. Microscopy and computational studies probe the 3D interior of the beads. The relative contributions that the capture and detection of moieties, analyte size, and bead porosity make to signal distribution and intensity are reported. Agarose pore sizes ranging from 45 to 620 nm are examined and those near 140 nm provide optimal transport characteristics for rapid (<15 min) tests. The system exhibits efficient (99.5%) detection of bead‐bound analyte along with low (≈2%) nonspecific immobilization of the detection probe for carcinoembryonic antigen assay. Furthermore, the role analyte dimensions play in signal distribution is explored, and enhanced methods for assay building that consider the unique features of biomarker size are offered.     

A Critical Review of the Quality and Safety of BADGE-Based Epoxy Coatings for Cans: Implications for Legislation on Epoxy Coatings for Food Contact

BADGE-based epoxy resins have been commercially available for more than 40 years. They are extremely versatile, finding applicationS in many fields in both thermal and ambient cure applications. The present review focuses on their use in the food industry as surface coatings for food and beverage cans, and in particular on their chemical stability in relation to their toxicology and sensorial effects on foods. The implications of these properties of epoxy resins for prospective EU legislation on plastic coatings for food contact is discussed.     

A transparent hybrid of nanocrystalline cellulose and amorphous calcium carbonate nanoparticles

Nanocellulose hybrids are promising candidates for biodegradable multifunctional materials. Hybrids of nanocrystalline cellulose (NCC) and amorphous calcium carbonate (ACC) nanoparticles were obtained through a facile chemical approach over a wide range of compositions. Controlling the interactions between NCC and ACC results in hard, transparent structures with tunable composition, homogeneity and anisotropy.     

Telescoping Languages: A Strategy for Automatic Generation of Scientific Problem-Solving Systems from Annotated Libraries

As machines and programs have become more complex, the process of programming applications that can exploit the power of high-performance systems has become more difficult and correspondingly more labor-intensive. This has substantially widened the software gap—the discrepancy between the need for new software and the aggregate capacity of the workforce to produce it. This problem has been compounded by the slow growth of programming productivity, especially for high-performance programs, over the past two decades. One way to bridge this gap is to make it possible for end users to develop programs in high-level domain-specific programming systems. In the past, a major impediment to the acceptance of such systems has been the poor performance of the resulting applications. To address this problem, we are developing a new compiler-based infrastructure, called TeleGen, that will make it practical to construct efficient domain-specific high-level languages from annotated component libraries. We call these languages telescoping languages, because they can be nested within one another. For programs written in telescoping languages, high performance and reasonable compilation times can be achieved by exhaustively analyzing the component libraries in advance to produce a language processor that recognizes and optimizes library operations as primitives in the language. The key to making this strategy practical is to keep compile times low by generating a custom compiler with extensive built-in knowledge of the underlying libraries. The goal is to achieve compile times that are linearly proportional to the size of the program presented by the user, rather than to the aggregate size of that program plus the base libraries.