Optimizing control of simulated moving beds--linear isotherm

A new optimization based adaptive control strategy for simulated moving beds (SMBs) is proposed. A linearized reduced order model, which accounts for the periodic nature of the SMB process, is used for online optimization and control. The manipulated variables are the four inlet flow rates, the outputs are the raffinate and extract concentrations. Concentration measurements at the raffinate and extract outlets are used as the feedback information. The state estimate from the periodic Kalman filter is used for the prediction of the outlet concentrations over a chosen horizon. Predicted outlet concentrations are the basis for the calculation of the optimal input adjustments, which maximize the productivity and minimize the desorbent consumption subject to constraints on product purities. The realization of this concept is discussed and the implementation on a virtual eight column SMB platform is assessed, in the case of binary linear systems. For a whole series of typical plant disturbances it is shown that the proposed approach is effective in minimizing off-spec products and in achieving optimal SMB operation, also in the case where there are significant model uncertainties.     

S(N)1-like reactions of bicyclic alpha-amino ethers with sulfur,nitrogen, and carbon nucleophiles. Synthesis of 1-azabicyclo[3.2.2]nonanes functionalized at carbon C2 and C6 with complete stereocontrol

[reaction: see text] In the presence of nucleophiles, Lewis acid mediated cleavage of alpha-amino ethers derived from quincorine and quincoridine affords a variety of C2-substituted and C6-vinylated 1-azabicyclo[3.2.2]nonanes. These are enantiopure and are formed in S(N)1-like reactions with complete stereocontrol. There is no leakage into 2-Nu en route to product 1-Nu or vice versa. Me(3)SiCN provides new Strecker-type alpha-amino nitriles. In the presence of TTMPP-BF(3).OEt(2), the ketene acetal Me(2)C=C(OMe)OSiMe(3) delivers enantiopure bicyclic beta-amino acid esters.     

Synthesis of benzaldehyde-functionalized LewisX trisaccharide analogs for glyco-SAM formation

LewisX (Le^x) antigen based carbohydrate–carbohydrate interactions are mediated by complexation of metal ions. Although theoretical studies about the influence of participating hydroxyl groups in the Le^x trisaccharide head group (Galβ(1-4)[Fucα(1-3)]GlcNAc) could gave same rudimental information about the basic mechanism behind this interaction, a little is known about orientation and configuration of the hydroxyl groups required for the specific interaction mediated by Ca²⁺ complexation. Therefore, there is a need of non-natural derivatives to provide detailed information about the requirements for hydroxyl group arrangement in Le^x head group surface plasmon resonance and gold nanoparticle techniques have shown to be powerful tools to investigate carbohydrate–carbohydrate interactions. Benzaldehyde-functionalized glycans can be used for attachment to both gold nanoparticles and surface plasmon resonance sensor surfaces. Therefore, seven benzaldehyde equipped Le^x analogs including the natural trisaccharide were synthesized utilizing convergent approach. The derivatives were applied in ongoing carbohydrate–carbohydrate interaction studies by surface plasmon resonance experiments to prove theoretical postulate about the structural requirements of hydroxyl group arrangements in Le^x trisaccharides.     

The stereochemistry of glycolipids. A key for understanding membrane functions?

A Commentary on the paper ”Studies on liquid‐crystalline glycosides" by Volkmar Vill, Thomas Böcker, Joachim Thiem and Fred Fischer. First published in Liquid Crystals, 6, 349‐356 (1989).     

Formation of Glyco-Functionalized Platinum Complexes by Cross-Metathesis and Evaluation of Their Efficacy in Inhibition of Lung Tumor Cell Lines

Syntheses of carbohydrate-functionalized platinum complexes resembling presently employed cytostatics were performed. Mono-allylated sugar substrates obtained in two steps from glucose and galactose were connected with 2-allyl diethyl malonate by cross-metathesis. Following hydrogenation and acidic cleavage of the ester and alkylidene functionalities gave dicarboxylated glycoconjugates, which were transformed into their diammine platinum complexes. The antitumor activities of these platinum complexes were checked by sensitivity testing with 11 lung cancer cell lines. The novel glucose-platinum complex proved to be comparable to the drug carboplatin.     

Ferrier glycosylation for synthesis of O- and S-glycopeptides

Abstract

Ferrier glycosylation could be employed for the syntheses of a range of unsaturated O- as well as S-glycopeptides. Thus, featuring high yields and in many cases convincing diastereomeric excesses, an efficient protocol for formation of this class of compounds was established.     

Finite Element Based Micro-mechanical Modeling of Interphase in Filler Reinforced Elastomers

Characteristic properties of elastomers can be tailored by embedding them with filler particles. Along with enhancing the overall properties of the composite, filler particles also induce some inelastic effects. In this paper, a finite element computational model is used to study the effect of microstructure morphology in filled elastomers, on its macroscopic large deformation behavior. A multiphase material model that accounts for the hypothesis of shift in glass transition temperature in the vicinity of the filler particle is developed to simulate the interphase between the fillers and the matrix. It also accounts for the breakdown and re-aggregation of filler networks under cyclic loading. Examples at the microstructural level, demonstrating the dynamics of the interphase using the developed multiphase model have been successfully simulated. The obtained results are in good qualitative agreement with the Mullins effect. Therefore, computational experiments using this methodology enable the prediction of the experimentally observed softening behavior in filled elastomers based on its microstructure evolution.