Impact of adsorption isotherm parameters on the performance of enantioseparation using simulated moving bed chromatography

Often there are several chromatographic systems, i.e., combinations of mobile and stationary phases, available to solve a certain separation problem. Essential differences of these chromatographic systems are the separation factors and the efficiencies. For preparative applications in addition also the column saturation capacities and solubility limits are of importance. The impact of all these parameters appears to be rather well understood for conventional overloaded elution chromatography using a single column. In the last years the continuous simulated moving bed (SMB) process was increasingly used as a powerful alternative to batch elution since increased productivities and reduced solvent consumptions could be realised. However, the selection of suitable chromatographic systems is more sophisticated for this process. In this paper five different chromatographic systems capable of separating the enantiomers of mandelic acid are compared based on the achievable productivities using SMB chromatography. For these five systems the adsorption isotherms have been determined experimentally. Subsequently, an analysis of the SMB process was performed numerically using a well-established model.     

Thermodynamics of systems of (oxy)alcohols and (poly)ethers

In this work, as a contribution to the study of alkanol-alkane-ether systems, we study the systems containing hydroxyl and ether groups either in separate molecules or in the same molecule. Typical cases are: Pure oxyalkanols, alkanes + oxyalkanols, alkanols + ethers, alkanols + polyethers, and alkanols + monoethers of poly(ethylene glycol). The presence of the hydroxyl and ether groups in these systems gives rise to two types of hydrogen bonds: a self-association, or OH---OH interaction and a cross-association, or OH---O interaction. In the general case these interactions give rise to multiple hydrogen bonding structures or association network structures. Because of this the widely used association theories which invoke the presence of simple association complexes (dimers, trimers, etc.) are not easily applicable to these systems. In this work we discuss the use of a generalized statistical thermodynamic formalism for the hydrogen bonding of molecules having any number of hydroxyl and/or ether groups. It is based on a recently developed equation-of-state type theory of hydrogen bonding networks in fluid systems. This formalism is subsequently reduced to the typical cases mentioned before. Experimental literature data are used for testing both the pure component- and the mixture - formalism.     

Structural Characterization of Non-Oxide Chalcogenide Glasses using Solid State NMR

In spite of the long-standing importance of non-oxide chalcogenide glasses in infrared optics and semiconductor technology, concepts describing the structural principles governing glass formation in these systems are just emerging. Most recently, modern quantitative solid state NMR techniques have offered new unique insights into the structural organization of these systems. In this review, we discuss the basic principles of various experimental approaches and their application to boron-silicon, -and phosphorus chalcogenide glasses.     

Detection of slightly soluble systems by means of organized media in flow-injection analysis

Species that are slightly soluble in water (reagents, analytes or reaction products can be used in hydrodynamic analytical systems by means of a judicious choice of an appropriate organized medium allowing one to operate in homogeneous media with the attendant advantages. In addition, these systems allow one to improve existing analytical methods and to develop new analytical procedures. Results obtained with two types of insoluble systems are presented: those provided by 1-(2-pyridylazo)-2-naphthol (PAN) and those originating from Arsenazo III in a strongly acid medium. Detection in these systems is possible by working with an organized medium. New methods for the determination of thorium, uranium and rare-earth elements are proposed.     

Homoclinic motions in the vibrational spectra of floppy systems: the LiCN molecule

Recent experimental and theoretical methods allowed the efficient investigation of highly excited rovibrational states of molecular systems. At these levels of excitation the correspondence principle holds, and then classical mechanics can provide intuitive views of the involved processes. In this respect, we have recently shown that for completely hyperbolic systems, homoclinic motions, which are known to organize the classical chaotic region in Hamiltonian systems, imprint a clear signature in the corresponding highly excited quantum spectra. In this Communication we show that this result also holds in mixed systems, by considering an application to the floppy LiNCLiCN molecular system.     

The Role of Hydrogen Bond Donor on the Extraction of Phenolic Compounds from Natural Matrices Using Deep Eutectic Systems

Recently, deep eutectic systems (DESs) as extraction techniques for bioactive compounds have surfaced as a greener alternative to common organic solvents. In order to study the effect of these systems on the extraction of phenolic compounds from different natural sources, a comprehensive review of the state of the art was carried out. In a first approach, the addition of water to these systems and its effect on DES physicochemical properties such as polarity, viscosity, and acidity was investigated. This review studied the effect of the hydrogen bond donor (HBD) on the nature of the extracted phenolics. The effects of the nature of the HBD, namely carbon chain length as well as the number of hydroxyl, methyl, and carbonyl groups, have shown to play a critical role in the extraction of different phenolic compounds. This review highlights the differences between DES systems and systematizes the results published in the literature, so that a more comprehensive evaluation of the systems can be carried out before any experimental trial.     

Magnetism in disjoint/non-disjoint composite bands

Non-bonding degenerate systems with disjoint/non-disjoint composite bands are suggested. In these systems, one of the non-bonding bands is disjoint, and another is non-disjoint type. Whereas the Wannier functions in the former bands span no common atoms, the Wannier functions in the latter bands span common atoms. Regardless of the disjoint bands, these systems are predicted to be ferromagnetic due to non-trivial exchange interactions in the non-disjoint bands. The ferromagnetic interactions are supported by DFT calculations.     

Some aspects of stability of multiple emulsions in personal cleansing systems

The two dominant factors that were found to affect the stability of multiple emulsions in high HLB surfactant systems are the osmotic pressure imbalance between the internal aqueous phase and the external aqueous phase, and the adsorption/desorption characteristics of the emulsifier/surfactant film at the oil/water interface. Synergistic interaction between the low HLB emulsifier and the high HLB surfactant that produces very low interfacial tension of the order of 10(-2) mN/m at the oil/water interface was found to occur in some of the systems investigated. Long term stability was observed in multiple emulsion containing these systems. However, no synergy was observed in systems in which either the oil or the emulsifier, or both, contained unsaturated chains. In fact, desorption of the adsorbed surfactant film was observed in systems containing unsaturated chains. The observed desorption from the interface of the emulsifier in these systems was attributed mainly to the inability of the unsaturated chains to form a close packed, condensed interfacial film. Presence of closely packed, condensed interfacial film is necessary to prevent solubilization of the adsorbed low HLB emulsifier by the high HLB surfactant. Multiple emulsions prepared using systems containing unsaturated hydrocarbons were highly unstable.     

Light-induced shape morphing of thin films

Shape transformation of thin two-dimensional sheets into three-dimensional structures using light is of great interest for remotely controlled fabrication, surface modulation, and actuation. Over the last few decades, significant efforts have been made to develop material systems incorporating photochemical or photothermal elements to drive deformation in response to illumination. However, the full extent of the interplay between chemistry, optics, and mechanics in these materials is poorly understood. In this review, we introduce principles of shape morphing in these systems by considering the underlying physics of photoinduced stresses and how these have been used in recent literature. In addition, we provide a critical overview of the important design characteristics of both photochemical and photothermal system and offer our view on the open opportunities and challenges in this rapidly growing field.     

Study on clarithromycin lactobionate based dual selector systems for the enantioseparation of basic drugs in capillary electrophoresis

In this paper, the use of clarithromycin lactobionate, a kind of antibiotic chiral selector, in combination with four neutral cyclodextrin derivatives (glucose‐β‐cyclodextrin, hydroxyethyl‐β‐cyclodextrin, methyl‐β‐cyclodextrin and hydroxypropyl‐β‐cyclodextrin) was reported for the first time. As a result, these dual systems gave much better resolution of nefopam (the Rs increased to 3.58, 2.72, 1.49 and 1.42, respectively) compared to the single systems. The effects of buffer pH and selector concentration on the separation of nefopam were also investigated. Additionally, some other basic drugs including metoprolol, atenolol, propranolol, bisoprolol, esmolol and ritodrine were tested for the investigation and evaluation of the enantiorecognition capability of the four dual systems. As expected, the synergistic effect was observed in four systems. Different results of these dual systems were also summarized.     

Photoisomerization of a carbocyanine derivative in the reverse phases of a block copolymer: evidence for the existence of water droplets

In an attempt to understand the nature of water present in the reverse phases of aggregates formed with the triblock copolymer poly(ethylene oxide)(20)-poly(propylene oxide)(70)-poly(ethylene oxide)(20) (P123) and also investigate how these confined environments influence the rates of photoisomerization, fluorescence lifetimes and quantum yields of a carbocyanine derivative--3,3'-diethyloxadicarbocyanine iodide (DODCI)--were measured in these systems over the temperature range of 293-318 K. Three different copolymer-oil-water compositions were chosen such that the mole ratio of water to copolymer (W) spans the range of 50-150. In these systems, butyl acetate was used as the oil or the nonpolar component. It has been noticed that in all three systems the fluorescence decays of DODCI comprise a long component whose contribution is 85-90%, and this has been ascribed to the fraction of solute solubilized in the core region where hydrated poly(ethylene oxide) units are present. A short-decay component is associated with the remaining fraction, and its values match with those measured in water, indicating that the water present in these reverse phases is in the form of droplets. The photoisomerization rate constants of DODCI located in the core regions of the reverse phases are identical in the three systems at a given temperature and similar to the ones obtained in normal phases of P123. The reasons for the observed behavior have been discussed.     

Phase structures of microemulsions

Microemulsions were subject to numerous studies during the last decades, mainly because of their potential with respect to applications, but they are also interesting model systems for statistical mechanics. This is due to their rather complicated phase behaviour and the fascinating microstructures encountered in microemulsion forming systems. In the present contribution new developments in the investigation and understanding of these microstructures will be outlined.     

Effect of electrostatic field on the polymer chain in the quaternized reaction of polyvinylpyridine with alkyl halides

In order to discuss the electrostatic-field effect on a polymer reaction, the quaternization of poly-4-vinylpyridine–benzyl chloride (system I) was compared to that of poly-γ-chloromethylstyrene–γ-picoline (system II). In these two systems, the reaction initially proceeded according to the simple second-order kinetics. However, after the degree of quaternization exceeded 20–30 mole-%, a deviation from simple second-order kinetics occurred. In system I negative deviation occurred, while in system II positive deviation occurred. These phenomena occurred even though the solvent or the initial concentrations of the reactants were changed. The reasons for these phenomena are given below. In system I, the quaternized pyridine nitrogens prevented the benzyl chloride from approaching the unquaternized pyridine nitrogens. However, in system II the free γ-picoline was attracted by the quaternized chloro-γ-methyl site. Furthermore, the point at which the deviation occurred was determined by the degree of chloromethylation. All these results suggest that the effect of an electrostatic field must be presumed in these two systems.     

The Development of Functional Group Tolerant Romp Catalysts

Since the discovery that transition metals salts mixed with organoaluminum reagents catalyze the polymerization of ethylene to crystalline polyethylene, organo-metallic complexes and reagents have played a major role in the polymer industry [1]. Over the past 20 years a tremendous amount has been learned about the structures and mechanisms of reactions of complexes related to those proposed to be active in these systems [2]. In the related area of olefin metathesis and ring-opening metathesis polymerization (ROMP), metal carbenes and metallacycles were proposed intermediates, and over the past few years a number of complexes with these structures that will catalyze the olefin metathesis reaction have been prepared and studied [3]. In contrast to the ill-defined classical catalysts based on Ziegler-type catalysts, these are living polymerization systems. This was first observed using Tebbe-type reagents [4].     

Photochemistry of supramolecular systems containing C60

Fullerenes have been used successfully in the covalent assembly of supramolecular systems that mimic some of the electron transfer steps of photosynthetic reaction centers. In these constructs C60 is most often used as the primary electron acceptor; it is linked to cyclic tetrapyrroles or other chromophores which act as primary electron donors in photoinduced electron transfer processes. In artificial photosynthetic systems, fullerenes exhibit several differences from the superficially more biomimetic quinone electron acceptors. The lifetime of the initial charge-separated state in fullerene-based molecules is, in general, considerably longer than in comparable systems containing quinones. Moreover, photoinduced electron transfer processes take place in non-polar solvents and at low temperature in frozen glasses in a number of fullerene-based dyads and triads. These features are unusual in photosynthetic model systems that employ electron acceptors such as quinones, and are more reminiscent of electron transfer in natural reaction centers. This behavior can be attributed to a reduced sensitivity of the fullerene radical anion to solvent charge stabilization effects and small internal and solvent reorganization energies for electron transfer in the fullerene systems, relative to quinone-based systems.     

Representation of cusps in a hyperspherical basis set

The wave functions of Coulomb systems have cusps at points corresponding to two particle coelescences. In this paper, we derive series representing the cusps in terms of hyperspherical harmonics multiplied by functions of the hyperradius. When the hyperspherical method is applied to Coulomb systems, the harmonics which appear in these series should be included in the hyperangular basis set.     

Molecular and Supramolecular Multiredox Systems

The design and synthesis of molecular and supramolecular multiredox systems have been summarized. These systems are of great importance as they can be employed in the next generation of materials for energy storage, energy transport, and solar fuel production. Nature provides guiding pathways and insights to judiciously incorporate and tune the various molecular and supramolecular design aspects that result in the formation of complex and efficient systems. In this review, we have classified molecular multiredox systems into organic and organic-inorganic hybrid systems. The organic multiredox systems are further classified into multielectron acceptors, multielectron donors and ambipolar molecules. Synthetic chemists have integrated different electron donating and electron withdrawing groups to realize these complex molecular systems. Further, we have reviewed supramolecular multiredox systems, redox-active host-guest recognition, including mechanically interlocked systems. Finally, the review provides a discussion on the diverse applications, e. g. in artificial photosynthesis, water splitting, dynamic random access memory, etc. that can be realized from these artificial molecular or supramolecular multiredox systems.