Scheduling at coal handling facilities using Simulated Annealing

The main thrust of this study is the operational scheduling of the continuous coal handling and blending processes when considering multiple, and sometimes conflicting, objectives. A widely applicable generic goal programming model is proposed. Furthermore, assumptions regarding the certainty of demand during different periods are challenged, endeavoring to provide more robust schedules in a largely stochastic environment. As the study aims to provide scheduling solutions to any coal handling facility, the Simulated Annealing metaheuristic is proposed to ensure that acceptably good solutions for large instances of the generic model can be found in reasonable computational time. The generic approach and its suggested application will be valuable not only in the coal handling environment, but also in the continuous product manufacturing/blending or continuous material handling environment.     

Closed solutions of boundary-value problems of coupled thermoelasticity

Coupled equations of thermoelasticity take into account the effect of nonuniform heating on the medium deformation and that of the dilatation rate on the temperature distribution. As a rule, the coupling coefficients are small and it is assumed, sometimes without proper justification, that the effect of the dilatation rate on the heat conduction process can be neglected. The aim of the present paper is to construct analytical solutions of some model boundary-value problems for a thermoelastic bounded body and to determine the body characteristic dimensions and the medium thermomechanical moduli forwhich it is necessary to take into account that the temperature and displacement fields are coupled. We consider some models constructed on the basis of the Fourier heat conduction law and the generalized Cattaneo-Jeffreys law in which the heat flux inertia is taken into account. The solution is constructed as an expansion in a biorthogonal system of eigenfunctions of the nonself-adjoint operator pencil generated by the coupled equations of motion and heat conduction. For the model problem, we choose a special class of boundary conditions that allows us to exactly determine the pencil eigenvalues.     

Homogeneous tandem catalysis of the bis‐(diphenylphosphino)‐amine/chromium tetramerization catalyst with metallocene catalysts

Homogeneous tandem catalysis of the bis(diphenylphoshino)amine‐chromium oligomerization catalyst with the metallocenes Ph₂C(Cp)(9‐Flu)ZrCl₂ and rac‐EtIn₂ZrCl₂, is discussed. GC, CRYSTAF, and ¹³C NMR analysis of the products obtained from reactions at constant temperatures show that during tandem catalysis, α‐olefins, mainly 1‐hexene and 1‐octene, are produced from ethylene by the oligomerization catalyst and subsequently built into the polyethylene chain. At 40 °C the Cr/PNP catalyst acts as a tetramerization catalyst while the polymerization catalyst activity is low. Copolymerization of ethylene and the in situ produced α‐olefins have also been carried out by increasing the temperature from 40 °C, where primarily oligomerization takes place, to above 100 °C, where polymerization becomes dominant. The melting temperature of the polymer is dependent on the catalyst and cocatalyst ratios as well as on the temperature gradient followed during the reaction, while the presence of the oligomerization catalyst reduces the activity of the polymerization catalyst. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6847–6856, 2006     

Spatially inhomogeneous crystallinity in heterogeneous ethylene‐α‐olefin copolymers

The crystallinity development in heterogeneous ethylene‐1‐butene copolymers is compared with that in ethylene copolymers, with more bulky 1‐heptene as a comonomer. The thermal transitions of the 1‐heptene based copolymers persistently occur at higher temperatures than of the corresponding 1‐butene copolymers. The earlier crystallization onset is reflected in thicker primary crystals, which in turn are associated with the presence of longer ethylene sequences because of the inaccessibility of 1‐heptene to sterically shielded catalytic sites. In addition, the 1‐heptene based copolymers are characterized by a higher degree of primary crystallinity, whereas the 1‐butene copolymers exhibit more prominent secondary crystallization. The 1‐butene based copolymers thus have a less heterogeneous chemical composition distribution. At high comonomer contents, the highly heterogeneous nature of the 1‐heptene copolymers is emphasized by a more pronounced presence of low crystalline spherulite inclusions accomplished by the liquid–liquid phase separation of dissimilar polymeric chains before crystallization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3000–3018, 2005     

Role of Cationization and Multimers Formation for Diastereomers Differentiation by Ion Mobility-Mass Spectrometry

Stereochemistry plays an important role in biochemistry, particularly in therapeutic applications. Indeed, enantiomers have different biological activities, which can have important consequences. Many analytical techniques have been developed in order to allow the identification and the separation of stereoisomers. Here, we focused our work on the study of small diastereomers using the coupling of traveling wave ion mobility and mass spectrometry (TWIMS-MS) as a new alternative for stereochemistry study. In order to optimize the separation, the formation of adducts between diastereomers (M) and different alkali cations (X) was carried out. Thus, monomers [M + X]⁺ and multimers [2M + X]⁺ and [3M + X]⁺ ions have been studied from both experimental and theoretical viewpoints. Moreover, it has been shown that the study of the multimer [2Y + M + Li]⁺ ion, in which Y is an auxiliary diastereomeric ligand, allows the diastereomers separation. The combination of cationization, multimers ions formation, and IM-MS is a novel and powerful approach for the diastereomers identification. Thus, by this technique, diastereomers can be identified although they present very close conformations in gaseous phase. This work presents the first TWIMS-MS separation of diastereomers, which present very close collision cross section thanks to the formation of multimers and the use of an auxiliary diastereomeric ligand.

The influence of mass imperfections on the evolution of standing waves in slowly rotating spherical bodies

Standing waves can exist as stable vibrating patterns in perfect structures such as spherical bodies, and inertial rotation of the body causes precession (Bryan's effect). However, an imperfection such as light mass anisotropy destroys the standing waves. In this paper, an imperfection is introduced in the form of light mass anisotropy for a vibrating, slowly rotating spherical body. Assuming this light mass imperfection throughout this paper, the effects of slow rotation and light isotropic viscous damping are considered in a system of variables consisting of the amplitudes of principal and quadrature vibrating patterns, the angle of the rotation of the vibrating pattern (called the precession angle) and the phase shift of the vibrating pattern. We demonstrate how a combination of both qualitative and quantitative analysis (using, inter alia, the method of averaging) predicts that the inertial angular rate does not influence changes with time in the amplitudes of the principal and quadrature vibrations or the phase shift. The light mass imperfection causes changes with time which appear to be of a damped oscillatory nature for both the quadrature component as well as the principal component. The precession angular rate appears to depend on the inertial angular rate as well as the quadrature component of the vibration but is not influenced by the damping factor. It is not directly proportional to the inertial angular rate as is the case for a perfect isotropically damped structure. If the quadrature component is not suppressed, then a “capture effect” appears to occur, namely that the precession angle will not grow at a constant rate but is “captured” and shows periodic behaviour. It is evident that the damping factor does not influence changes with time in the phase shift and that the mass imperfection substantially influences these changes. The phase shift appears to be negative, strictly decreasing and unbounded.     

Spectroscopic characteristics of praseodymium-doped cubic double sodium-yttrium fluoride crystals Na0.4Y0.6F2.2:Pr3+. Intensities of optical transitions and luminescence kinetics

Using the Bridgman-Stockbarger technique, we have grown a series of cubic crystals Na_0.4Y_0.6F_2.2:Pr³⁺ (NYF:Pr³⁺) with a content of praseodymium in the range of 0.04–9 at %. We have determined the composition of crystals, evaluated their optical quality, and found the incorporation coefficient of Pr³⁺ ions into the Na_0.4Y_0.6F_2.2 matrix (K _Pr ～ 0.9). We have examined optical spectra of NaYF:Pr³⁺ crystals at room and low (7 K) temperatures in the range of 200–2500 nm. The low-temperature absorption spectra of NYF:Pr³⁺ crystals have been shown to consist of broad weakly structured bands. Based on the analysis of low-temperature absorption spectra, the structure of the Stark splitting of praseodymium levels has been represented in terms of a model of “quasi-centers,” which are characterized by an inhomogeneous broadening of Stark components. From experimental absorption cross-section spectra at T = 300 K, we have calculated oscillator strengths for transitions from the ground state ³ H ₄ to excited multiplets ³ H ₅, ³ H ₆, ³ F _j (j = 2, 3, 4), ¹ G ₄, ¹ D ₂, and (³ P _j ,¹ I ₆) (j = 0, 1, 2). Using the Judd-Ofelt method, we have determined intensity parameters Ω _t and found that Ω₂ = 0, Ω₄ = 4.4 × 10^?20, and Ω₆ = 2.28 × 10^?20 cm². With these values, we have calculated the probabilities of radiative transitions, the branching coefficients, and the lifetimes of the radiative levels ¹ D ₂ and ³ P ₀. The probabilities of multiphonon nonradiative transitions in NYF:Pr³⁺ crystals have been estimated. Using the method of kinetic spectroscopy with selective excitation, we have investigated the luminescence decay kinetics of praseodymium from the ³ P ₀ and ¹ D ₂ levels upon their selective resonant excitation by nanosecond laser pulses. The inference has been made that Na_0.4Y_0.6F_2.2:Pr³⁺ crystals are processable; admit doping by praseodymium in high concentrations; and, with respect to all their radiative characteristics, can be potentially considered as active media for converters of optical radiation and solid-state continuously tunable lasers in the visible range.     

Kinetic optimisation of the reversed phase liquid chromatographic separation of rooibos tea (Aspalathus linearis) phenolics on conventional high performance liquid chromatographic instrumentation

Rooibos tea, produced from the endemic South African shrub Aspalathus linearis, has various health-promoting benefits which are attributed to its phenolic composition. Generating reliable, quantitative data on these phenolic constituents is the first step towards documenting the protective effects associated with rooibos tea consumption. Reversed phase liquid chromatographic (RP-LC) methods currently employed in the quantitative analysis of rooibos are, however, hampered by limited resolution and/or excessive analysis times. In order to overcome these limitations, a systematic approach towards optimising the RP-LC separation of the 15 principal rooibos tea phenolics on a 1.8 μm phase using conventional HPLC instrumentation was adopted. Kinetic plots were used to obtain the optimal configuration for the separation of the target analytes within reasonable analysis times. Simultaneous optimisation of temperature and gradient conditions provided complete separation of these rooibos phenolics on a 1.8 μm C18 phase within 37 min. The optimised HPLC–DAD method was validated and successfully applied in the quantitative analysis of aqueous infusions of unfermented and fermented rooibos. Major phenolic constituents of fermented rooibos were found to be a phenylpropanoid phenylpyruvic acid glucoside (PPAG), the dihydrochalcone C-glycoside aspalathin, the flavones isoorientin and orientin, and a flavonol O-diglycoside tentatively identified as quercetin-3-O-robinobioside. Content values for PPAG, ferulic acid and quercetin-3-O-robinobioside in rooibos are reported here for the first time. Mass spectrometric (MS) and tandem MS detection were used to tentatively identify 13 additional phenolic compounds in rooibos infusions, including a new luteolin-6-C-pentoside-8-C-hexoside and a novel C-8-hexosyl derivative of aspalathin reported here for the first time.     

Metalloenzyme-Mediated Thiol-Yne Addition Towards Photoisomerizable Fluorescent Dyes

Proteins are able to irreversibly assemble biologically active ligands from building blocks bearing complementary reactive functions due their spatial proximity, through a kinetic target-guided synthetic process (also named in situ click chemistry). Although linkages thus formed are mostly passive, some of them have shown to significantly contribute to the protein binding through for instance hydrogen bonding and stacking interactions. Biocompatible reactions and click chemistry are a formidable source of inspiration for developing such new protein-directed ligations. This study reports a proximity-induced thiol-yne synthesis of carbonic anhydrase inhibitors. Not only this example widens the arsenal of kinetic target-guided synthesis (KTGS) eligible reactions, but the obtained product displayed unsuspected photophysical properties. The corresponding vinyl sulfide linkage conjugated to a coumarin core proved to be engaged in a monodirectional Z to E photoisomerization process. Further investigations guided by theoretical calculations showed that fine-tuning of the nature of the substituents on the coumarin moiety allows to obtain a bidirectional photochemical process, thus discovering a new photoswitching moiety, displaying moreover fluorescence properties. Due to the spectral tunability of coumarin derivatives, this work should open new opportunities for the design of vinyl sulfide-based photoswitch systems with modular photophysical properties.