Information and Entropy Flow in the Kalman–Bucy Filter

We investigate the information theoretic properties of Kalman–Bucy filters in continuous time, developing notions of information supply, storage and dissipation. Introducing a concept of energy, we develop a physical analogy in which the unobserved signal describes a statistical mechanical system interacting with a heat bath. The abstract universe comprising the signal and the heat bath obeys a non-increase law of entropy; however, with the introduction of partial observations, this law can be violated. The Kalman–Bucy filter behaves like a Maxwellian demon in this analogy, returning signal energy to the heat bath without causing entropy increase. This is made possible by the steady supply of new information. In a second analogy the signal and filter interact, setting up a stationary non-equilibrium state, in which energy flows between the heat bath, the signal and the filter without causing any overall entropy increase. We introduce a rate of interactive entropy flow that isolates the statistical mechanics of this flow from marginal effects. Both analogies provide quantitative examples of Landauers Principle.     

RNA cleavage and inhibition of protein synthesis by bleomycin

Bleomycin is a clinically used antitumor antibiotic long thought to function therapeutically at the level of DNA cleavage. Recently, it has become clear that bleomycin can also cleave selected members of all major classes of RNA. Using the computer program COMPARE to search the database established by the Anticancer Drug Screening Program of the National Cancer Institute, a possible mechanism-based correlation was found between onconase, an antitumor ribonuclease currently being evaluated in phase III clinical trials, and the chemotherapeutic agent bleomycin. Following these observations, experimentation revealed that bleomycin caused tRNA cleavage and DNA-independent protein synthesis inhibition in rabbit reticulocyte lysate and when microinjected into Xenopus oocytes. The correlation of protein synthesis inhibition to the previously reported site-specific RNA cleavage caused by bleomycin supports the thesis that RNA cleavage may constitute an important element of the mechanism of action of bleomycin.     

Potential of atmospheric pressure chemical ionization source in GC‐QTOF MS for pesticide residue analysis

The potential applications of a new atmospheric pressure source for GC‐MS analysis have been investigated in this work. A list of around 100 GC‐amenable pesticides, which includes organochlorine, organophosphorus and organonitrogenated compounds, has been used to evaluate their behavior in the new source. Favoring the major formation of the molecular ion in the source has been the main goal due to the wide‐scope screening possibilities that this fact brings in comparison with the traditional, highly fragmented electron ionization spectra. Thus, the addition of water as modifier has been tested as a way to promote the generation of protonated molecules. Pesticides investigated have been classified into six groups according to their ionization/fragmentation behavior. Four of them are characterized by the abundant formation of the protonated molecule in the atmospheric pressure source, mostly being the base peak of the spectrum. These results show that wide‐scope screening could be easily performed with this source by investigating the presence of the protonated molecule ion, MH+. The developed procedure has been applied to pesticide screening in different food samples (nectarine, orange and spinach) and it has allowed the presence of several pesticides to be confirmed such as chlorpyriphos ethyl, deltamethrin and endosulfan sulfate. The availability of a quadrupole time‐of‐flight instrument made it feasible to perform additional MS/MS experiments for both standards and samples to go further in the confirmation of the identity of the detected compounds. Results shown in this paper have been obtained using a prototype source which exhibits promising features that could be applied to other analytical problems apart from those illustrated in this work. Copyright © 2010 John Wiley & Sons, Ltd.     

Investigation of uremic analytes in hemodialysate and their structural elucidation from accurate mass maps generated by a multi‐dimensional liquid chromatography/mass spectrometry approach

Historically, structural elucidation of unknown analytes by mass spectrometry alone has involved tandem mass spectrometry experiments using electron ionization. Most target molecules for bioanalysis in the metabolome are unsuitable for detection by this previous methodology. Recent publications have used high‐resolution accurate mass analysis using an LTQ‐Orbitrap with the more modern approach of electrospray ionization to identify new metabolites of known metabolic pathways. We have investigated the use of this methodology to build accurate mass fragmentation maps for the structural elucidation of unknown compounds. This has included the development and validation of a novel multi‐dimensional LC/MS/MS methodology to identify known uremic analytes in a clinical hemodialysate sample. Good inter‐ and intra‐day reproducibility of both chromatographic stages with a high degree of mass accuracy and precision was achieved with the multi‐dimensional liquid chromatography/tandem mass spectrometry (LC/MS/MS) system. Fragmentation maps were generated most successfully using collision‐induced dissociation (CID) as, unlike high‐energy CID (HCD), ions formed by this technique could be fragmented further. Structural elucidation is more challenging for large analytes >270 Da and distinguishing between isomers where their initial fragmentation pattern is insufficiently different. For small molecules (<200 Da), where fragmentation data may be obtained without loss of signal intensity, complete structures can be proposed from just the accurate mass fragmentation data. This methodology has led to the discovery of a selection of known uremic analytes and two completely novel moieties with chemical structural assignments made. Copyright © 2009 John Wiley & Sons, Ltd.     

Review

Abstract

Scattering Theory (Aspects of Scattering Processes in Atomic, Nuclear and Particle Physics) Edited by A. O. Barut Gordon and Breach Science Publishers Inc., 1969, pp. viii + 431.     

Dielectrowetting driven spreading of droplets

The wetting of solid surfaces can be modified by altering the surface free energy balance between the solid, liquid, and vapor phases. Here we show that liquid dielectrophoresis induced by nonuniform electric fields can be used to enhance and control the wetting of dielectric liquids. In the limit of thick droplets, we show theoretically that the cosine of the contact angle follows a simple voltage squared relationship analogous to that found for electrowetting on dielectric. Experimental observations confirm this predicted dielectrowetting behavior and show that the induced wetting is reversible. Our findings provide a noncontact electrical actuation process for meniscus and droplet control.     

Zur Bestimmung und Trennung des Titans

Ohne Zusammenfassung     

Suzuki cross-coupling reactions using reverse-phase glass beads in aqueous media

Reverse-phase glass beads have been employed in Suzuki reactions to provide, in aqueous media, a route to diverse polar substrates in good yield and with low levels of palladium leaching.