Hemicellulose Hydrolysis in the Presence of Heterogeneous Catalysts

A prominent autocatalytic effect in the hydrolysis of hemicelluloses was observed in the presence of heterogeneous cation-exchange catalysts, Amberlyst 15 and Smopex 101. The kinetic models proposed were based on the reactivities of the non-hydrolysed sugar monomer units and the increase of the rate constant as the reaction progresses and the degree of polymerization decreases. General kinetic models were derived and the kinetic parameters, describing the autocatalytic effect, were determined by non-linear regression analysis. The kinetic model explained very well the overall kinetics, as well as the product distribution in the hydrolysis of hemicelluloses.

     

IR-sintering of ink-jet printed metal-nanoparticles on paper

Sintering of printed metal nanoparticles can be made not only by conventional heating, but also by, e.g., electrical, microwave, plasma, laser and flash lamp annealing. We demonstrate sintering by using low-cost incandescent lamps as an effective way of obtaining highly conductive contacts of two types of ink-jet printed metal-nanoparticle inks on paper; both alkanethiol protected gold nanoparticles and a commercially available silver nanoparticle ink. This low-cost roll-to-roll compatible sintering process is especially suitable on paper substrates because of the high diffuse reflectance, relatively high thermal stability and low thermal conductivity of paper. A volume resistivity of around 10 μΩ cm was achieved of the inkjetted silver nanoparticles within 15 s of exposure to an IR lamp, which corresponds to a conductivity of 10-20% of that of bulk silver. Too long exposure time and too high intensity, however, lead to darkening of the paper fibers. Both the crack formation and the coffee ring effect of the inkjet printed gold nanoparticles were, furthermore, found to be reduced on paper as compared to glass or plastic substrates.     

Textured strontium titanate layers on platinum by atomic layer deposition

Formation of textured strontium titanate (STO) layers with large lateral grain size (0.2-1 μm) and low X-ray reflectivity roughness (~ 1.36 nm) on Pt electrodes by industry proven atomic layer deposition (ALD) method is demonstrated. Sr(t-Bu₃Cp)₂, Ti(OMe)₄ and O₃ precursors at 250 °C were used to deposit Sr rich STO on Pt/Ti/SiO₂/Si ∅200 mm substrates. After crystallization post deposition annealing at 600 °C in air, most of the STO grains showed a preferential orientation of the {001} plane parallel to the substrate surface, although other orientations were also present. Cross sectional and plan view transmission electron microscopy and electron diffraction analysis revealed more than an order of magnitude larger lateral grain sizes for the STO compared to the underlying multicrystalline {111} oriented platinum electrode. The combination of platinum bottom electrodes with ALD STO(O₃) shows a promising path towards the formation of single oriented STO film.     

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.     

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.     

Priorities for Fresh Water Use Purposes in Selected Countries with Policy Implications

Priorities in water use purposes were studied by a two-phase questionnaire in 11 countries/regions on five continents with different water resources and use, socio-economic and cultural conditions. The first phase involved three regions: East Africa (1988), the Baltic region (1994) and Finland (1993, 2001). In the second phase (2001–02), water use purposes were to be viewed ‘as they are’ and ‘as they should be’. On average, community water supply was ranked first, nature conservation second and hydropower third. Priorities varied less than originally anticipated. Priorities should also be remembered in integrated water resources management.     

Xylose hydrogenation: kinetic and NMR studies of the reaction mechanisms

Hydrogenation of xylose over Raney nickel was studied in a batch reactor. A pseudo-homogeneous kinetic model was able to prognose the xylose and xylitol concentrations rather well. The obtained fit for the activation energies suggests that external diffusion limitations are absent in our experimental conditions. The sugar equilibria studies gave new information about the temperature dependence of the –β-pyranose equilibria. It was found that the equilibria in D₂O follows an S-shaped curve, the equilibria being shifted towards the -form at higher temperatures.     

Mechanistic model for kinetics of propene hydroformylation with Rh catalyst

Hydroformylation of propene to isobutyraldehyde and n‐butyraldehyde was studied in the kinetic regime in a semibatch stainless steel reactor at 85–115°C and 1–15 bar pressure in 2,2,4‐trimethyl‐1,3‐pentanediol monoisobutyrate solvent with rhodium catalyst cyclohexyl diphenylphosphine as a ligand, which showed lower normal/isometric aldehyde ratio (n/i) than previously studied triphenylphosphine. The rate was pressure and Rh concentration dependent. The regioselectivity was conversion independent; however, dependent on the ligand concentration, as higher ligand concentration promoted isobutyraldehyde formation. The influence of ligand concentration on regioselectivity was investigated. A kinetic model was proposed based on the mechanism of alkene hydroformylation and compared with experimental observations. Numerical data fitting was performed showing good agreement of reaction rates and regioselectivity with experimental data. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Effects of ethanol to water ratio in feed solution on the crystallinity of spray-dried lactose

In the present study, the effects of ethanol to water ratio in feed solution on the physical properties of spray-dried alpha-lactose monohydrate were evaluated. Crystallinity of the spray-dried lactose was determined by isothermal microcalorimetry (IMC) and by differential scanning calorimetry (DSC). Water content of the spray-dried lactose was determined by thermogravimetric analysis and the surface area was evaluated by Brunauer, Emmett, and Teller (BET) method. The crystallinity of spray-dried lactose varied from 0% to 100%, depending on the ratio of ethanol to water in the feed solution. Lactose spray dried from pure ethanol was 100% crystalline and contained hydrate water. Lactose spray dried from pure water was 100% amorphous. The feed solution substantially affected the ratio of surface water to hydrate water, as the content of surface water increased and hydrate water decreased, while the crystallinity of spray-dried lactose decreased. Surface area of the spray-dried lactose increased as a function of amorphous content.