Propene and 1-Octene Hydroformylation with Silica-Supported, Ionic Liquid-Phase (SILP) Rh-Phosphine Catalysts in Continuous Fixed-Bed Mode

Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium)phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF₆], on a silica support. The catalysts were active in continuous gas- and liquid-phase hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h^-1 for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase hydroformylation using SILP catalysts.     

Hydrogen bonding,miscibility, crystallization,and thermal stability in blends of biodegradable polyhydroxyalkanoates and polar small molecules of 4‐tert‐butylphenol

The hydrogen bonding, miscibility, crystallization, and thermal stability of poly(3‐hydroxybutyrate) (PHB)/4‐tert‐butylphenol (BOH) blends and poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) [P(3HB‐3HHx)]/BOH blends were investigated by Fourier transform infrared (FTIR) spectroscopy, solid‐state¹³C‐NMR, differential scanning calorimetry, wide‐angle X‐ray diffraction (WAXD), and thermogravimetric analysis. The results of FTIR spectroscopy and solid‐state¹³C‐NMR show that intermolecular hydrogen bonds existed between the two components in the blends and that the interaction was caused by the carbonyl groups in the amorphous phase of both polyesters and the hydroxyl groups of BOH. With increasing BOH content, the chain mobility of both the PHB and P(3HB‐3HHx) components was improved. After the samples were quenched, the detected single glass‐transition temperatures decreased with composition, indicating that both PHB/BOH and P(3HB‐3HHx)/BOH were miscible blends in the melt. Moreover, as BOH content increased, the melting temperatures of PHB and P(3HB‐3HHx) clearly decreased, which implied that their crystallization was suppressed by the addition of BOH. Although the crystallinity of PHB and P(3HB‐3HHx) components decreased with increasing BOH content in the blends, their crystal structures were hardly affected after they were blended with BOH, which was further proven by WAXD results. In addition, the thermal stability of PHB was improved by a smaller amount of BOH.     

Plasma desorption mass spectrometry, an analytical tool in protein engineering: characterization of modified insulins

Californium-252 plasma desorption mass spectrometry (PDMS) hasbeen employed for the characterization of a series of humaninsulin derivatives in order to evaluate the performance ofthis technique as an analytical tool in protein engineering.Several of the characterized modifications result in a 1 a.m.u.mass change. The precision in mass determination obtainableby PDMS analysis is not sufficient for unambiguous verificationof such modifications based on the molecular weight alone. Itis, however, possible to carry out in situ enzymatic digestionof the sample. Subsequent PDMS analysis will in most cases revealif the modification has been introduced as intended.     

Visual learning and classification of human epithelial type 2 cell images through spontaneous activity patterns

Identifying the presence of anti-nuclear antibody (ANA) in human epithelial type 2 (HEp-2) cells via the indirect immunofluorescence (IIF) protocol is commonly used to diagnose various connective tissue diseases in clinical pathology tests. As it is a labour and time intensive diagnostic process, several computer aided diagnostic (CAD) systems have been proposed. However, the existing CAD systems suffer from numerous shortcomings due to the selection of features, which is commonly based on expert experience. Such a choice of features may not work well when the CAD systems are retasked to another dataset. To address this, in our previous work, we proposed a novel approach that learns a set of filters from HEp-2 cell images. It is inspired by the receptive fields in the mammalian's vision system, since the receptive fields can be thought as a set of filters for similar shapes. We obtain robust filters for HEp-2 cell classification by employing the independent component analysis (ICA) framework. Although, this approach may be held back due to one particular problem; ICA learning requires a sufficiently large volume of training data which is not always available. In this paper, we demonstrate a biologically inspired solution to address this issue via the use of spontaneous activity patterns (SAP). The spontaneous activity patterns, which are related to the spontaneous neural activities initialised by the chemical release in the brain, are found as the typical stimuli for the visual cell development of newborn animals. In the classification system for HEp-2 cells, we propose to model SAP as a set of small image patches containing randomly positioned Gaussian spots. The SAP image patches are generated and mixed with the training images in order to learn filters via the ICA framework. The obtained filters are adopted to extract the set of responses from a HEp-2 cell image. We then employ regions from this set of responses and stack them into “cubic regions”, and apply a classification based on the correlation information of the features. We show that applying the additional SAP leads to a better classification performance on HEp-2 cell images compared to using only the existing patterns for training ICA filters. The improvement on classification is particularly significant when there are not enough specimen images available in the training set, as SAP adds more variations to the existing data that makes the learned ICA model more robust. We show that the proposed approach consistently outperforms three recently proposed CAD systems on two publicly available datasets: ICPR HEp-2 contest and SNPHEp-2.     

Sky Based Light Metering for High Dynamic Range Images

Image calibration requires both linearization of pixel values and scaling so that values in the image correspond to real‐world luminances. In this paper we focus on the latter and rather than rely on camera characterization, we calibrate images by analysing their content and metadata, obviating the need for expensive measuring devices or modeling of lens and camera combinations. Our analysis correlates sky pixel values to luminances that would be expected based on geographical metadata. Combined with high dynamic range (HDR) imaging, which gives us linear pixel data, our algorithm allows us to find absolute luminance values for each pixel—effectively turning digital cameras into absolute light meters. To validate our algorithm we have collected and annotated a calibrated set of HDR images and compared our estimation with several other approaches, showing that our approach is able to more accurately recover absolute luminance. We discuss various applications and demonstrate the utility of our method in the context of calibrated color appearance reproduction and lighting design.     

Spectral Ray Differentials

Light refracted by a dispersive interface leads to beautifully colored patterns that can be rendered faithfully with spectral Monte‐Carlo methods. Regrettably, results often suffer from chromatic noise or banding, requiring high sampling rates and large amounts of memory compared to renderers operating in some trichromatic color space. Addressing this issue, we introduce spectral ray differentials, which describe the change of light direction with respect to changes in the spectrum. In analogy with the classic ray and photon differentials, this information can be used for filtering in the spectral domain. Effectiveness of our approach is demonstrated by filtering for offline spectral light and path tracing as well as for an interactive GPU photon mapper based on splatting. Our results show considerably less chromatic noise and spatial aliasing while retaining good visual similarity to reference solutions with negligible overhead in the order of milliseconds.     

Towards an Unbiased Comparison of CC,BCC, and FCC Lattices in Terms of Prealiasing

In the literature on optimal regular volume sampling, the Body‐Centered Cubic (BCC) lattice has been proven to be optimal for sampling spherically band‐limited signals above the Nyquist limit. On the other hand, if the sampling frequency is below the Nyquist limit, the Face‐Centered Cubic (FCC) lattice was demonstrated to be optimal in reducing the prealiasing effect. In this paper, we confirm that the FCC lattice is indeed optimal in this sense in a certain interval of the sampling frequency. By theoretically estimating the prealiasing error in a realistic range of the sampling frequency, we show that in other frequency intervals, the BCC lattice and even the traditional Cartesian Cubic (CC) lattice are expected to minimize the prealiasing. The BCC lattice is superior over the FCC lattice if the sampling frequency is not significantly below the Nyquist limit. Interestingly, if the original signal is drastically undersampled, the CC lattice is expected to provide the lowest prealiasing error. Additionally, we give a comprehensible clarification that the sampling efficiency of the FCC lattice is lower than that of the BCC lattice. Although this is a well‐known fact, the exact percentage has been erroneously reported in the literature. Furthermore, for the sake of an unbiased comparison, we propose to rotate the Marschner‐Lobb test signal such that an undue advantage is not given to either lattice.     

On‐the‐fly generation and rendering of infinite cities on the GPU

In this paper, we present a new approach for shape‐grammar‐based generation and rendering of huge cities in real‐time on the graphics processing unit (GPU). Traditional approaches rely on evaluating a shape grammar and storing the geometry produced as a preprocessing step. During rendering, the pregenerated data is then streamed to the GPU. By interweaving generation and rendering, we overcome the problems and limitations of streaming pregenerated data. Using our methods of visibility pruning and adaptive level of detail, we are able to dynamically generate only the geometry needed to render the current view in real‐time directly on the GPU. We also present a robust and efficient way to dynamically update a scene's derivation tree and geometry, enabling us to exploit frame‐to‐frame coherence. Our combined generation and rendering is significantly faster than all previous work. For detailed scenes, we are capable of generating geometry more rapidly than even just copying pregenerated data from main memory, enabling us to render cities with thousands of buildings at up to 100 frames per second, even with the camera moving at supersonic speed.     

Automatic generation of tourist brochures

We present a novel framework for the automatic generation of tourist brochures that include routing instructions and additional information presented in the form of so‐called detail lenses. The first contribution of this paper is the automatic creation of layouts for the brochures. Our approach is based on the minimization of an energy function that combines multiple goals: positioning of the lenses as close as possible to the corresponding region shown in an overview map, keeping the number of lenses low, and an efficient numbering of the lenses. The second contribution is a route‐aware simplification of the graph of streets used for traveling between the points of interest (POIs). This is done by reducing the graph consisting of all shortest paths through the minimization of an energy function. The output is a subset of street segments that enable traveling between all the POIs without considerable detours, while at the same time guaranteeing a clutter‐free visualization.     

Bleaching of indigo-dyed denim fabric by electrochemical formation of hypohalogenites in situ

The use of hypochlorite, formed in situ by anodic oxidation of sodium chloride solution, for bleaching indigo-dyed denim has been studied at room temperature and at 50 °C. A direct relationship between the charge flow applied and the bleaching effect was observed. This enables consistent oxidative bleaching to be achieved by controlling the electrochemical process. The use of mixed anolytes containing small concentrations of bromide ions enhanced the bleaching effect considerably, even after lowering the temperature to room temperature. The molar concentration of bromide ions required was much lower than that of chloride in the anolyte.