Frequency and phase estimation in time series with quasi periodic components

In this article, we consider frequency and phase estimation in a noisy oscillation with potentially non‐constant phase increments resulting from an underlying non‐constant frequency. A maximum periodogram method on segments is used to estimate the time‐varying frequency and a subsequent least squares approach to estimate the phase. A key problem addressed in this article is the question how to set up a meaningful concept of asymptotic statistics for this model. This problem is solved by a special infill asymptotics concept. We use this concept to prove consistency and asymptotic normality of the estimates. Furthermore, the phase estimate is compared to the Hilbert transform in a simulation.     

Artificial Light Regulation of an Allosteric Bienzyme Complex by a Photosensitive Ligand

The artificial regulation of proteins by light is an emerging subdiscipline of synthetic biology. Here, we used this concept to photocontrol both catalysis and allostery within the heterodimeric enzyme complex imidazole glycerol phosphate synthase (ImGP‐S). ImGP‐S consists of the cyclase subunit HisF and the glutaminase subunit HisH, which is allosterically stimulated by substrate binding to HisF. We show that a light‐sensitive diarylethene (1,2‐dithienylethene, DTE)‐based competitive inhibitor in its ring‐open state binds with low micromolar affinity to the cyclase subunit and displaces its substrate from the active site. As a consequence, catalysis by HisF and allosteric stimulation of HisH are impaired. Following UV‐light irradiation, the DTE ligand adopts its ring‐closed state and loses affinity for HisF, restoring activity and allostery. Our approach allows for the switching of ImGP‐S activity and allostery during catalysis and appears to be generally applicable for the light regulation of other multienzyme complexes.     

NONLINEAR PI CONTROLLER FOR pH PROCESS

The control of pH is one of the most difficult challenges in the process industry because of the severe nonlinearities and high precision required in manipulating the flow rate. The Wiener model, which consists of a linear dynamic element followed by a nonlinear static element, is used for representing such nonlinear processes. Piecewise continuous polynomials are used for mapping the nonlinear static gain accurately. A nonlinear PI controller was designed based on the Wiener model. Simulation results on the nonlinear mathematical model are presented to highlight the superior performance of the Wiener model based nonlinear PI controller in comparison to that of the local linear PI controller. The performance of the nonlinear PI controller was further improved upon by using the method of inequalities to obtain a single set of PI controller settings that takes into account the parametric variations in the linear dynamic element at different operating points. Simulation and experimental results are presented to support the work.     

Porous concrete as a template for the synthesis of porous carbon materials

The potential of industrial porous concrete for using as a template for the synthesis of porous carbon materials has been investigated. Carbon replicas of porous concrete have been prepared by carbonization of sucrose. The pores of the resulting carbon materials range from the macropore to the micropore region, pointing to a hierarchy.     

Controlled reversible debundling of single-walled carbon nanotubes by photo-switchable dendritic surfactants

Stimulus responsive surfactants based on dendritic glycerol azobenzene conjugates were used to solubilize and debundle single-walled carbon nanotubes in aqueous media. Their debundling property as well as their reaggregation behavior upon irradiation with light was examined and light triggered reversible bundling and precipitation are shown.     

Evaluation of polycaprolactone − poly‐D,L‐lactide copolymer as biomaterial for breast tissue engineering

The potential of the copolymer polycaprolactone‐co‐ poly‐d ,l ‐lactic acid (PCLLA ) as a biomaterial for scaffold‐based therapy for breast tissue engineering applications was assessed. First, the synthesized PCLLA was evaluated for its processability by means of additive manufacturing (AM ). We found that the synthesized PCLLA could be fabricated into scaffolds with an overall gross morphology and porosity similar to that of polycaprolactone. The PCLLA scaffolds possessed a compressive Young's modulus (ca 46 kPa ) similar to that of native breast (0.5 ? 25 kPa ), but lacked thermal stability and underwent thermal degradation during the fabrication process. The PCLLA scaffolds underwent rapid degradation in vitro which was characterized by loss of the scaffolds' mechanical integrity and a drastic decrease in mass‐average molar mass (M _w) and number‐average molar mass (M _n) after 4 weeks of immersion in phosphate buffer solution maintained at 37 °C. The tin‐catalysed PCLLA scaffold was also found to have cytotoxic effects on cells. Although the initial mechanical properties of the PCLLA scaffolds generally showed potential for applications in breast tissue regeneration, the thermal stability of the copolymer for AM processes, biocompatibility towards cells and degradation rate is not satisfactory at this stage. Therefore, we conclude that research efforts should be geared towards fine‐tuning the copolymer synthesizing methods. © 2016 Society of Chemical Industry     

Evaluation of dynamic modulus measurement for C/C-SiC composites at different temperatures

The determination of elastic properties at application temperature is fundamental for the design of fibre reinforced ceramic composite components. An attractive method to characterize the flexural modulus at room and high temperature under specific atmosphere is the nondestructive Resonant Frequency Damping Analysis (RFDA). The objective of this paper was to evaluate and validate the modulus measurement via RFDA for orthotropic C/C-SiC composites at the application temperature. At room temperature flexural moduli of C/C-SiC with 0/90° reinforcement were measured under quasi-static 4-point bending loads and compared with dynamic moduli measured via RFDA longitudinally to fibre direction. The dynamic modulus of C/C-SiC was then measured via RFDA up to 1250°C under flowing inert gas and showed an increase with temperature which fitted with literature values. The measured fundamental frequencies were finally compared to those resulting from numerical modal analyses. Dynamic and quasi-static flexural moduli are comparable and the numerical analyses proved that bending modes are correctly modeled by means of dynamic modulus measured via RFDA. The nondestructive RFDA as well as the numerical modeling approach are suitable for evaluation of C/C-SiC and may be transferred to other fibre reinforced ceramic composite materials.     

Peculiarities of Phase Transitions and Structure Formation in a Ternary Al-Cu-Ni Alloy with Four-Phase Peritectic Reaction

The structure formation in peritectic Al-4.5at.%Cu-11at.%Ni ternary alloy with four-phase peritectic reaction was investigated using the quantitative phase-field model of eutectic growth. This model, extended to an arbitrary number of phases, guarantees the stability requirements on individual interfaces. The thermal noise terms disturb the stability and produce the heterogeneous nucleation of secondary phases in accordance to the energetic and concentration conditions. In our recent work it was shown that in differential thermal analysis (DTA) experiments specific microstructure parts in Al-4.5at.%Cu-11at.%Ni alloy with a four-phase peritectic reaction were observed, which cannot be explained by Scheil calculation or simple phase-field modeling. In this work, it was found by numerical experiments that, due to the formation of anisotropic quasi-primary Al₃Ni₂ crystals and the suppression of the nucleation of (Al) phase, the eutectic-like coupled growth of Al₃Ni₂ and Al₃Ni phases can be observed. In addition, at further cooling the anisotropic shape of quasi-secondary Al₃Ni crystals promotes the nucleation of the (Al) phase. The simulated final structure is comparable to the experimental one which is characterized by large Al₃Ni₂ crystals enveloped by the Al₃Ni phase.     

The effect of oxygen and the reduction temperature of the Pt/Al2O3 catalyst in enantioselective hydrogenation of 1-phenyl-1,2-propanedione

The effect of oxygen and catalyst reduction temperature in enantioselective hydrogenation of 1-phenyl-1,2-propanedione over commercial Pt/Al₂O₃ catalyst was investigated. Dichloromethane was used as solvent. The catalyst was modified in situ with (−)-cinchonidine. Relatively high enantiomeric excesses (65%) of (R)-1-hydroxy-1-phenyl-2-propanone were obtained with the solvent used as received, i.e. containing traces of dissolved oxygen and other impurities. Dichloromethane dissociated partially on the Pt/Al₂O₃ surface causing desorption of methane, ethene and HCl from the catalyst during TPD according to mass spectrometric analysis. Under anaerobic conditions the reaction rate was low giving only about 40% enantiomeric excesses of (R)-1-hydroxy-1-phenyl-2-propanone. When injecting 5 mm³ of oxygen into the reactor a beneficial effect was observed (i.e. higher reaction rate and enantiomeric excess) in comparison with anaerobic conditions. Poisoning effect of oxygen was observed when injecting 500 mm³ of oxygen into the reactor. Effect of catalyst reduction temperature was studied at three different temperatures (170, 400 and 455°C). Highest reaction rates and enantiomeric excesses were obtained with the catalyst reduced at 400°C. Methane was desorbed from the catalyst at temperatures between 263 and 383°C which could be the explanation for the lower activity of the catalyst reduced at 170°C. It was demonstrated that small amounts of oxygen can have a beneficial effect in enantioselective hydrogenation of 1-phenyl-1,2-propanedione and also that catalyst reduction temperature plays an important role in obtaining high enantiomeric excesses.