Nonlinear model predictive control based on piecewise linear Hammerstein models

This paper develops a nonlinear model predictive control (MPC) algorithm for dynamic systems represented by piecewise linear (PWL) Hammerstein models. At each sampling instant, the predicted output trajectory is linearized online at an assumed input trajectory such that the control actions can be easily calculated by solving a quadratic programming optimization problem, and such linearization and optimization may be repeated a few times for good linear approximation accuracy. A three-step procedure is developed to linearize a PWL function, where the derivatives of a PWL function are obtained by a computationally efficient look-up table approach. Unlike many existing MPC algorithms for Hammerstein systems, it does not require the inversion of static nonlinearity and can directly cope with input constraints even in multivariable systems. Two benchmark chemical reactors are studied to illustrate the effectiveness of the proposed algorithm.     

Assessment of predictive control performance using fractal measures

This paper presents novel approach to the task of control performance assessment. Proposed approach does not require any a priori knowledge on process model and uses control error time series data using nonlinear dynamical fractal persistence measures. Notion of the rescaled range R/S plots with estimation of Hurst exponent is applied. Crossover phenomenon is observed in data being investigated and discussed. Paper starts with industrial engineering rationale. Review of the control error histogram is followed by statistical analysis of probabilistic distribution functions (PDFs). Lévy \(\alpha \)-stable PDF parameters seem to be best fitted. They directly lead to the fractal analysis using Hurst exponents and R/S plot crossover points. The evaluation aims at performance of the generalized predictive control (GPC) and discusses freshly introduced loop performance quality sensitivity against design parameters of the GPC controller.     

Complexation of aminoglutethimide with native and modified cyclodextrins

Complexations of R(+) and RS(+/?)aminoglutethimide (AGT), the drug used in a treatment of breast and prostate cancer with native and modified cyclodextrins (α‐CD, β‐CD, γ‐CD, 2,6‐di‐O‐methyl‐β‐CD (DM‐β‐CD), 2,3,6‐tri‐O‐methyl‐β‐CD (TM‐β‐CD) and carboxymethyl‐β‐CD (CM‐β‐CD)) were studied. The stability constants were determined with UV–Vis spectrophotometric method at pH 9.0. The NMR data obtained for TM‐β‐CD suggest that the complexation of AGT is possible from both sides of CD molecule. This was confirmed by molecular dynamic simulations. Copyright © 2009 John Wiley & Sons, Ltd.     

Asymmetric Dearomative (3+2)-Cycloaddition Involving Nitro-Substituted Benzoheteroarenes under H-Bonding Catalysis

In our studies, the organocatalytic 1,3-dipolar cycloaddition between 2-nitrobenzofurans or 2-nitrobenzothiophene and N-2,2,2-trifluoroethyl-substituted isatin imines has been developed. The reaction has been realized by employing bifunctional organocatalysis, with the use of squaramide derivative being crucial for the stereochemical efficiency of the process. The usefulness of the cycloadducts obtained has been confirmed in selected transformations, including aromative and non-aromative removal of the nitro group.     

Saffron yellow: characterization of carotenoids by high performance liquid chromatography with electrospray mass spectrometric detection

Saffron is one of the oldest natural dyestuffs and is obtained from the dried stigmata of Crocus sativus L. Nowadays, saffron is considered as an invaluable spice of golden‐yellow hue, a precious ingredient in the Eastern and Mediterranean cuisines. It is characterized by a bitter taste that is caused by the chemical properties of its constituents. The yellowness of saffron results from the presence of crocins (glycosyl esters of crocetin), its main color compounds, which are examined in the present study in the crude methanol extracts by high performance liquid chromatography (HPLC) coupled with spectrophotometric and electrospray mass spectrometric detection (HPLC–UV‐Vis–ESI MS). This technique allowed the separation and identification of trans‐ and cis‐isomers of crocins. Their mass spectra registered in the negative ion mode comprised the quasi‐molecular and fragment ions, as well as a range of other ions. Doubly charged ions were found for trans‐isomers only, due to the high symmetry of their molecules. Modification of the eluent allowed the identification of several signals corresponding to adduct ions of crocins with the used additives. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and Crystal Structures of Two New Schiff Base Hydrazones Derived from Biphenyl-4-Carbohydrazide

Abstract  

The crystal structures of two novel Schiff base hydrazones have been determined by means of the X-ray diffraction. These compounds: N′-[(E)-(2,5-dimethoxyphenyl)methylidene]biphenyl-4-carbohydrazide, C₂₂H₂₀N₂O₃ (1) and N′-[(E)-(4-fluorophenyl)methylidene]biphenyl-4-carbohydrazide, C₂₀H₁₅FN₂O (2), are the first structurally characterized biphenyl derivatives of phenylmethylidene-carbohydrazide. Both compounds crystallize in the monoclinic space groups, 1 in P2₁/c space group with a = 13.987(2) ?, b = 16.426(3) ?, c = 8.214(2) ?, β = 98.12(2)°, and 2 in C2/c with a = 37.163(5) ?, b = 10.696(2) ?, c = 8.098(2) ?, β = 101.18(2)°. Both molecules have very similar bond lengths and angles pattern, even in the differently substituted phenyl ring. However, the conformations of the molecules differ significantly, the more crowded molecule 1 is much more folded than 2. The dihedral angle between the terminal ring planes is 56.17(6)° in 1 while in 2 it is as small as 2.83(14)°. In both structures relatively short and linear N–H···O hydrogen bonds (created by the best available hydrogen bond donor and acceptor) connect molecules into the chains along the unit cell parameter of ca. 8 ? in length. The next stage of the crystal architecture determination, the secondary interactions, are however quite different: in 1 there are almost solely dispersion van der Waals interactions while in 2 some more specific C–H···F and C–H···π interactions are also involved in the crystal packing.     

Differentiation of fluoronitroaniline isomers by negative-ion electrospray mass spectrometry

Tetra- and trifluoronitroanilines were studied by electrospray ionization mass spectrometry. These compounds gave signals only in the negative-ion mode. It was found that the so-called 'in-source' fragmentation, induced by cone voltage increase, enables differentiation of isomers. For para-nitroanilines, in contrast to ortho derivatives, the loss of NO(2) was the most favored process and other fragment ions were characterized by low abundances. For trifluoro conjugates the substitution pattern of aromatic ring by fluorine atoms also affected their fragmentation patterns. For example, in 2,3,6-trifluoro-4-nitroaniline, in contrast to 2,3,5-trifluoro-4-nitroaniline, efficient NO loss, followed by HF loss, took place.