Kinetic Monte Carlo modeling of CO desorption and adsorption on Pd(110) surface

Desorption and adsorption of carbon monoxide on Pd(110) is modeled and simulated, aiming at gaining atomic level understanding of experimentally observed rates. The model parameters are fitted to reproduce the temperature programmed desorption spectra and molecular beam surface scattering data. Desorption turns out to be best described as thermally activated, the activation energy depending on the detailed nearest neighbor site occupation configuration. For a good fit, the adsorption induced surface reconstruction needs to be included in the model. Also, desorption needs to be modeled with a precursor state included. However, surface diffusion was not found to be essential. With these ingredients the coverage dependent sticking coefficient can be successfully simulated in the temperature range from 300 to 500 K. Furthermore, the experimentally observed saturation coverage—temperature dependence is correctly predicted from the balance between simultaneous adsorption and desorption.     

Capillary supercritical fluid chromatography-atmospheric pressure chemical ionization mass spectrometry of γ- and α-linolenic acid containing triacylglycerols in berry oils

The effect of the γ-linolenic acid (18:3n-6) residue on the elution of triacylglycerols on a 25% cyanopropyl-25% phenyl-50% methylpolysiloxane stationary phase was confirmed by using capillary supercritical fluid chromatography-atmospheric pressure chemical ionization mass spectrometry [cSFC-(APCI)MS]. The general elution rule on this stationary phase is that triacylglycerols having the same ACN+2n value coeluted (ACN-acyl carbon number and n=combined number of double bonds in the acyl chains). The different effect of γ- and α-linolenic acid residues on the retention of triacylglycerols and the use of cSFC-(APCI)MS allowed the study of the number of different linolenic acid residue isomer combinations in triacylglycerols with an identical ACN and degree of unsaturation. Stearidonic acid (18:4n-3) residue was found to have a similar effect on the retention behavior of triacylglycerols as that of γ-linolenic acid residue. The abundance of the [M-RCOO]⁺ ion, formed by the loss of one fatty acid moiety of a triacylglycerol, was found to be clearly higher in the case of γ-isomer of the linolenic acid than that of α-isomer in the identical regiospecific position. This indicates that the distance of the double bonds from the glycerol backbone in the acyl chain affects the stability of a triacylglycerol molecule in the (APCI)MS system. The triacylglycerol composition and the fatty acid combinations of triacylglycerols were found to be almost identical in black currant (Ribes nigrum) and alpine currant (R. alpinum) seed oils.     

Restoring Coefficient Symmetry in Polyphase Implementation of Linear-Phase FIR Filters

Polyphase implementation of FIR filters effectively reduces the multiplication rate and data storage in a multirate system. However, the coefficients of the polyphase components are no longer symmetric even though the overall filter has a symmetric (or anti-symmetric) impulse response. In this paper, we introduce a new technique that recasts pairs of the original polyphase components as sums or differences of auxiliary pairs of symmetric and anti-symmetric impulse response filters. The coefficient symmetry of these auxiliary polyphase components can be fully exploited to reduce arithmetic complexity without undue complications. Our new technique makes use of the fact that the impulse responses of the non-symmetric polyphase components exist in time-reversed pairs which can be synthesized from pairs of symmetric and anti-symmetric impulse response filters. This results in a factor-of-two reduction in the number of multipliers required to implement the polyphase components.     

Efficient Multisplitting Revisited: Optima-Preserving Elimination of Partition Candidates

We consider multisplitting of numerical value ranges, a task that is encountered as a discretization step preceding induction and also embedded into learning algorithms. We are interested in finding the partition that optimizes the value of a given attribute evaluation function. For most commonly used evaluation functions this task takes quadratic time in the number of potential cut points in the numerical range. Hence, it is a potential bottleneck in data mining algorithms.We present two techniques that speed up the optimal multisplitting task. The first one aims at discarding cut point candidates in a quick linear-time preprocessing scan before embarking on the actual search. We generalize the definition of boundary points by Fayyad and Irani to allow us to merge adjacent example blocks that have the same relative class distribution. We prove for several commonly used evaluation functions that this processing removes only suboptimal cut points. Hence, the algorithm does not lose optimality.Our second technique tackles the quadratic-time dynamic programming algorithm, which is the best schema for optimizing many well-known evaluation functions. We present a technique that dynamically—i.e., during the search—prunes partitions of prefixes of the sorted data from the search space of the algorithm. The method works for all convex and cumulative evaluation functions.Together the use of these two techniques speeds up the multisplitting process considerably. Compared to the baseline dynamic programming algorithm the speed-up is around 50 percent on the average and up to 90 percent in some cases. We conclude that optimal multisplitting is fully feasible on all benchmark data sets we have encountered.     

Novel osteoconductive β-tricalcium phosphate/poly(L-lactide-co-e-caprolactone) scaffold for bone regeneration: a study in a rabbit calvarial defect

The advantages of synthetic bone graft substitutes over autogenous bone grafts include abundant graft volume, lack of complications related to the graft harvesting, and shorter operation and recovery times for the patient. We studied a new synthetic supercritical CO₂ –processed porous composite scaffold of β-tricalcium phosphate and poly(L-lactide-co-caprolactone) copolymer as a bone graft substitute in a rabbit calvarial defect. Bilateral 12?mm diameter critical size calvarial defects were successfully created in 18 rabbits. The right defect was filled with a scaffold moistened with bone marrow aspirate, and the other was an empty control. The material was assessed for applicability during surgery. The follow-up times were 4, 12, and 24 weeks. Radiographic and micro-CT studies and histopathological analysis were used to evaluate new bone formation, tissue ingrowth, and biocompatibility. The scaffold was easy to shape and handle during the surgery, and the bone-scaffold contact was tight when visually evaluated after the implantation. The material showed good biocompatibility and its porosity enabled rapid invasion of vasculature and full thickness mesenchymal tissue ingrowth already at four weeks. By 24 weeks, full thickness bone ingrowth within the scaffold and along the dura was generally seen. In contrast, the empty defect had only a thin layer of new bone at 24 weeks. The radiodensity of the material was similar to the density of the intact bone. In conclusion, the new porous scaffold material, composed of microgranular β-TCP bound into the polymer matrix, proved to be a promising osteoconductive bone graft substitute with excellent handling properties.

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On Learning and Cross-Validation with Decomposed Nyström Approximation of Kernel Matrix

The high computational costs of training kernel methods to solve nonlinear tasks limits their applicability. However, recently several fast training methods have been introduced for solving linear learning tasks. These can be used to solve nonlinear tasks by mapping the input data nonlinearly to a low-dimensional feature space. In this work, we consider the mapping induced by decomposing the Nyström approximation of the kernel matrix. We collect together prior results and derive new ones to show how to efficiently train, make predictions with and do cross-validation for reduced set approximations of learning algorithms, given an efficient linear solver. Specifically, we present an efficient method for removing basis vectors from the mapping, which we show to be important when performing cross-validation.     

Pyrolysis of Softwood Carbohydrates in a Fluidized Bed Reactor

In the present work pyrolysis of pure pine wood and softwood carbohydrates, namely cellulose and galactoglucomannan (the major hemicellulose in coniferous wood), was conducted in a batch mode operated fluidized bed reactor. Temperature ramping (5 °C/min) was applied to the heating until a reactor temperature of 460 °C was reached. Thereafter the temperature was kept until the release of non-condensable gases stopped. The different raw materials gave significantly different bio-oils. Levoglucosan was the dominant product in the cellulose pyrolysis oil. Acetic acid was found in the highest concentrations in both the galactoglucomannan and in the pine wood pyrolysis oils. Acetic acid is most likely formed by removal of O-acetyl groups from mannose units present in GGM structure.     

Leg deformities of oribatid mites as an indicator of environmental pollution

Oribatid mites have often been used as indicators of the degree of environmental pollution but few studies have assessed the effects of pollution at individual level. One possible indicator of environmental stress at individual level is structural malformations of exoskeleton. We studied whether a number of leg deformities in soil oribatid mites could be used as an indicator of the degree of heavy metal pollution or acidity in nature. For this purpose we collected soil samples in a well known pollution gradient of a Finnish Cu-Ni smelter. Heavy metals are common pollutants in the area. Ten focal oribatid species were inspected under microscope for deformations in their legs (missing, broken or deformed leg). Of the focal species only one (Chamobates cuspidatus) showed an increasing trend along the pollution gradient in the proportion of leg abnormalities but there were clear differences in proportions among species. We consider that leg deformities are not a good indicator of heavy metal exposure in the studied species. Our data suggest, however, that they may indicate spatial variation in soil pH. We also tested for the possible effects of pollution on oribatid species number and abundances. There were pollution-related differences in relative abundances of mites but not in the number of species. We discuss the relationship between soil pH, calcium requirements and skeletal malformations of oribatid mites.     

Locality kernels for sequential data and their applications to parse ranking

We propose a framework for constructing kernels that take advantage of local correlations in sequential data. The kernels designed using the proposed framework measure parse similarities locally, within a small window constructed around each matching feature. Furthermore, we propose to incorporate positional information inside the window and consider different ways to do this. We applied the kernels together with regularized least-squares (RLS) algorithm to the task of dependency parse ranking using the dataset containing parses obtained from a manually annotated biomedical corpus of 1100 sentences. Our experiments show that RLS with kernels incorporating positional information perform better than RLS with the baseline kernel functions. This performance gain is statistically significant. An erratum to this article can be found at