Interconversion of Lactose to Lactulose in Alkaline Environment: Comparison of Different Catalysis Concepts

Interconversion of lactulose to lactulose with the aim to determine and optimize the yield of ketose was carried out. Various homogenous and heterogeneous alkaline catalysts were applied (NaOH, MgO, hydrotalcite etc.). The selectivity and activity of the catalysts were compared. The results gave insight to the performance differences among the screened catalysts under the various reaction conditions. From the activity performance point of view, the conversion was limited by the formation of acidic end-products. In general, the selectivity decreased with conversion and the conversion-selectivity pattern was independent of the catalyst.     

Comparison of certain MINLP algorithms when applied to a model structure determination and parameter estimation problem

The maximum likelihood method is frequently used in parameter estimation. If the structure of the model is unknown, the maximization of the likelihood function can be replaced by minimizing an information criterion. One criterion that allows this to be done is Akaike’s information criterion (AIC). Minimizing the AIC is a mixed integer non-linear programming (MINLP) problem. In this paper, three different MINLP algorithms are compared in the solution of a simultaneous model structure determination and parameter estimation problem by minimizing the AIC criterion. The problem considered appears in quantitative Fourier transformed infra red (FTIR) spectroscopy where concentration estimates of certain gas components are to be obtained from measured absorbances at different wave numbers. The resulting problem is a large MINLP problem containing several hundreds, or even thousands, of variables including a huge number of possible model structures. It is, however, found that the studied algorithms solve the considered problem in quite a small number of iterations and a reasonable CPU-time.     

Monotonicity of approximate entropy during transition from awareness to unresponsiveness due to propofol anesthetic induction

The ability to monitor the physiological effects of sedative medication accurately is of interest in clinical practice. During the anesthetic agent driven transition to unresponsiveness, nonstationary changes such as signal amplitude variations appear in electroencephalography. In this paper, it is studied whether the application of the approximate entropy (ApEn) method to electroencephalographic (EEG) signal produces a monotonic response curve during the transition from awareness to unresponsiveness. Data from fourteen patients, undergoing propofol anesthetic induction were studied. To optimize the ApEn performance, different parameter choices were carefully evaluated. It was assumed with our protocol, that the level of anesthesia changes monotonically with the elapsed induction time. The monotonicity of the ApEn change was assessed with the prediction probability statistic (PK). The monotonicity of the ApEn time-series depends on the parameters employed in the algorithm and the varying signal amplitude. Depending on the parameter values, the median PK value ranged from 0.886 to 0.527. Thus, a good directionality and concordance was observed, but the nonstationarity of the signal affected the results. In conclusion, EEG-based ApEn measure shows a nonlinear response during propofol induction. With a judicious choice of parameters, a monotonic response is confirmed using PK statistic.     

Mind reading with regularized multinomial logistic regression

In this paper, we consider the problem of multinomial classification of magnetoencephalography (MEG) data. The proposed method participated in the MEG mind reading competition of ICANN’11 conference, where the goal was to train a classifier for predicting the movie the test person was shown. Our approach was the best among ten submissions, reaching accuracy of 68 % of correct classifications in this five category problem. The method is based on a regularized logistic regression model, whose efficient feature selection is critical for cases with more measurements than samples. Moreover, a special attention is paid to the estimation of the generalization error in order to avoid overfitting to the training data. Here, in addition to describing our competition entry in detail, we report selected additional experiments, which question the usefulness of complex feature extraction procedures and the basic frequency decomposition of MEG signal for this application.     

Infinite Photography: New Mathematical Model for High-Resolution Images

A new mathematical image model is introduced using the photographic process as the starting point. Images are represented as infinite sequences of photons allowing analysis at arbitrarily high resolution and leading to novel computational methods for processing, representation, transmission and storage of images. The resulting space of infinite photographs is proved to have a metric structure and to be intimately connected with bounded Borel measures. Theorems are proved indicating that the imaging power of the photographic process exceeds function spaces in the high resolution limit; this implies in particular that natural photographic images need to be modelled by generalized functions. Furthermore, computational results are presented to illustrate the novel algorithms based on photon sequences. The algorithms include stochastic halftoning, representation of cartoon images with outlines, anti-aliasing, blurring and singularity extraction.     

Stereochemistry of the hydroperoxides formed during autoxidation of CLA methyl ester in the presence of α-tocopherol

The initial steps in the autoxidation of CLA methyl ester are poorly understood. The aim of this study was to determine the stereochemistry of the hydroperoxides formed during autoxidation of CLA methyl ester in the presence of a good hydrogen atom donor. For this purpose, 9-cis, 11-trans CLA methyl ester was autoxidized in the presence of α-tocopherol under atmospheric oxygen at 40°C in the dark. The CLA methyl ester hydroperoxides were isolated, reduced to the corresponding hydroxy derivatives, and separated by HPLC. The stereochemistry of seven hydroxy-CLA methyl esters was investigated. The position of the hydroxy group was determined by GC-MS. The geometry as well as the position of the double bonds in the alkyl chain was determined by NMR. In addition, the ¹³C NMR spectra of six hydroxy-CLA methyl esters were assigned using COSY, gradient heteronuclear multiple bond correlation, gradient heteronuclear single quantum correlation, and total correlation spectroscopy experiments. The autoxidation of 9-cis, 11-trans CLA methyl ester in the presence of a good hydrogen atom donor is stereoselective in favor of one geometric isomer, namely the 13-(R,S)-hydroperoxy-9-cis, 11-trans-octadecadienoic acid methyl ester. Three types of conjugated diene hydroperoxides are formed as primary hydroperoxides: trans,trans hydroperoxides (12-OOH-8t,10t and 9-OOH-10t,12t), a cis,trans hydroperoxide with the trans double bond adjacent to the hydroperoxide-bearing carbon atom (13-OOH-9c,11t), and a new type of cis,trans lipid hydroperoxide with the cis double bond adjacent to the hydroperoxide-bearing carbon atom (8-OOH-9c,11t). In addition, three nonkinetic hydroperoxides (13-OOH-9t,11t, 8-OOH-9t,11t, and 9-OOH-10t,12c) are formed. This study supports the theory that CLA methyl ester autoxidizes at least partly through an autocatalytic free radical reaction. The complexity of the hydroperoxide mixture is due to formation of two different pentadienyl radicals. Moreover, the stereoslectivity in favor of one geometric isomer can be explained by the selectivity of the two previous steps: the preferential formation of a W-conformer of the pentadienyl radical over the Z-conformer, and regioselectivity of the oxygen addition to the pentadienyl radical.     

Preparation and Study of Pd Catalysts Supported on Activated Carbon Cloth (ACC) for Direct Synthesis of H2O2 from H2 and O2

Activated carbon cloths (ACCs) were used as supports for Pd catalysts. The catalyst preparation was carried out by the impregnation method using acidic solution of palladium dichloride (PdCl₂) as metal precursor. The effects of the oxidation state of the loaded metal, heat treatment of the catalysts in different atmosphere (H₂, air) at different temperatures and surface chemistry of the support on the catalyst characterizations and the catalytic activities were investigated. Wet oxidation of ACC was done by nitric acid in order to induce oxygen-containing surface functional groups. Surface chemistry of the support and oxidation state of the metallic phase was investigated by means of XPS, TPD, SEM, DTA and TGA tests. Direct synthesis of hydrogen peroxide from H₂ and O₂ was performed batch wise in a stainless steel autoclave. The reactions were conducted under high pressure (38 bar) at 0 °C and methanol was used as reaction medium. The direct synthesis results showed that the oxygen-containing surface functional groups increase the selectivity of the catalysts by reducing the rate of water production. Existence of the oxidized state of Pd (PdO) also makes the catalyst more selective than the corresponding zerovalent state (Pd0). PdO affected on selectivity by increasing the rate of H₂O₂ production and reducing the amount of production of water, simultaneously.     

Isomerization of α-Pinene Oxide Over Iron-Modified Zeolites

Fe-modified mordenite, ferrierite, Y, ZSM-5, ZSM-12 and beta zeolite catalysts were prepared by solid state ion-exchange and conventional liquid phase ion-exchange methods from aqueous solutions. Sn- modified H-beta-300 zeolite catalyst was prepared by the later method. The characterization of proton form, Fe and Sn modified zeolites was carried out using X-ray powder diffraction, scanning electron microscopy, Mössbauer spectroscopy with magnetic measurements, transmission electron microscopy, nitrogen adsorption, X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma spectroscopy, thermo-gravimetric analysis and FTIR spectroscopy using pyridine as a probe molecule. Isomerization of α-pinene oxide over the Fe and Sn modified zeolite catalysts was carried out in the liquid phase using a batch-wise glass reactor. Formation of campholenic aldehyde and fencholenic aldehyde were observed to be influenced by the structure, acidity of zeolite and contents of Fe and Sn, reaction temperature and the catalysts pretreatment.