Thermodynamics of catalytic formation of dimethyl ether from methanol in acidic zeolites

We present a theoretical study of the formation of the first intermediate, dimethyl ether, in the methanol to gasoline conversion within the framework of an ab initio molecular dynamics approach. The study is performed under conditions that closely resemble the reaction conditions in the zeolite catalyst including the full topology of the framework. The use of the method of thermodynamic integration allows us to extract the free-energy profile along the reaction coordinate. We find that the entropic contribution qualitatively alters the free-energy profile relative to the total energy profile. Different transition states are found from the internal and free energy profiles. The entropy contribution varies significantly along the reaction coordinate and is responsible for stabilizing the products and for lowering the energy barrier. The hugely inhomogeneous variation of the entropy can be understood in terms of elementary processes that take place during the chemical reaction. Our simulations provide new insights into the complex nature of this chemical reaction.     

On the existence of Analytic Semigroups Bounded on the Half-Disc in some Banach Algebras

Let G be a locally compact group. We show that L¹(G) does notcontain any analytic semigroups which are bounded on the half-disc,by using some facts about the analytic Radon-Nikodm propertyin Banach spaces. This solves a question raised by J. Esterle.     

Anion Recognition and Sensing: The State of the Art and Future Perspectives

Anion recognition chemistry has grown from its beginnings in the late 1960s with positively charged ammonium cryptand receptors for halide binding to, at the end of the millennium, a plethora of charged and neutral, cyclic and acyclic, inorganic and organic supramolecular host systems for the selective complexation, detection, and separation of anionic guest species. Solvation effects and pH values have been shown to play crucial roles in the overall anion recognition process. More recent developments include exciting advances in anion-templated syntheses and directed self-assembly, ion-pair recognition, and the function of anions in supramolecular catalysis.     

2-amidopyrroles and 2,5-diamidopyrroles as simple anion binding agents.

Four new 2-amidopyrroles and 2,5-diamidopyrroles have been synthesized and their anion complexation properties investigated. The crystal structures of these receptors have been elucidated and reveal hydrogen bonding in the solid state leading to dimer and network formation. Selectivity for oxo-anions has been demonstrated by (1)H NMR titration techniques.     

Geometric scaling effects on instrumental plate height in field flow fractionation

This paper examines geometric scaling models for field flow fractionation systems to understand how channel dimensions affect resolution and retention. Specifically, the changing contribution of the instrumental plate height during miniaturization of field flow fractionation (FFF) systems is reported. The work is directed towards determining the optimal geometrical parameters for miniaturization of field flow fractionation systems. The experimental relationship between channel height in FFF systems and instrumental plate heights is reported. FFF scaling models are modified to: (i) better clarify the dependence of plate height and resolution on channel height in FFF and (ii) include a more complete geometrical scaling analysis and model comparison in the low retention regime. Electrical field flow fractionation has been shown to benefit from miniaturization, so this paper focuses on that subtype, but surprisingly, the results also indicate the possibility of improvement in performance with miniaturization of other field flow fractionation systems including general FFF subtypes in which the applied field does not vary with channel height. This paper also discusses the potential role of more powerful microscale field flow fractionation systems as a new class of sample preparation units for micro-total-analysis systems (mu-TAS).     

Assisted desolvation as a key kinetic step for crystal growth

The crystallization of materials from a supersaturated solution is a fundamental chemical process. Although several very successful models that provide a qualitative understanding of the crystal growth process exist, in most cases the atomistic detail of crystal growth is not fully understood. In this work, molecular dynamics simulations of the morphologically most important surfaces of barite in contact with a supersaturated solution have been performed. The simulations show that an ordered and tightly bound layer of water molecules is present on the crystal surface. The approach of an ion to the surface requires desolvation of both the surface and the ion itself leading to an activated process that is rate limiting for two-dimensional nucleation to occur. However, desolvation on specific surfaces can be assisted by anions adsorbed on the crystal surface. This hypothesis, corroborated by crystallization and scanning electron microscopy studies, allows the rationalization of the morphology of barite crystals grown at different supersaturations.     

A microfabricated electrical SPLITT system

A growing need for methods to analyze and prepare monodisperse nanoparticles on an industrial scale exists and may be solved by the application of split flow thin fractionation (SPLITT) at the microscale. Microfluidic systems of this type have the ability to separate nanoparticles with high precision in a continuous manner. A miniaturized SPLITT system can be fabricated using standard microfabrication technologies, works in a continuous mode, and can be used as a sample preparation instrument in a micro-total-analysis-system (micro-TAS). In this paper, a miniaturized electrical SPLITT system, which separates particles continuously based on electrophoretic mobility, has been characterized. The advantages of miniaturization have been elucidated. The various aspects of the micro SPLITT system discussed in this paper can be broadly classified into: micro SPLITT system design, fluidics modeling to refine the splitter arrangements, and experimental characterization of the SPLITT system. The design of the micro SPLITT system has been elucidated focusing on the two designs that were implemented. Fluid modeling, used to arrive at a new SPLITT design, was done using a commercially available CFD package to investigate behavior of the fluid in the microchannel with various splitter arrangements. Testing was done with nanoparticles of varying diameter and electrophoretic mobilities to verify the modeling results and demonstrate functionality of the SPLITT system. Particles eluted from both outlets of the SPLITT system were characterized using AFM and SEM to verify the function of the system.