Influence of Process Parameters on the Reaction Kinetics of the Chromium‐Catalyzed Trimerization of Ethylene

In this paper we report the results of an extensive experimental kinetic study carried out on the novel ethylene trimerization catalyst system, comprising the chromium source [CrCl₃(thf)₃] (thf=tetrahydrofuran), a Ph₂P‐N(iPr)‐P(Ph)‐N(iPr)H (PNPNH) ligand (Ph=phenyl, iPr=isopropyl), and triethylaluminum (AlEt₃) as activator. It could be shown that the initial activity shows a first‐order dependency on the ethylene concentration. Also, a first‐order dependency was found for the catalyst concentration. The initial activity follows a typical Arrhenius behavior with an experimentally determined activation energy of 52.6 kJ mol^?1. At elevated temperatures (ca. 80 °C), a significant deactivation was observed, which can be tentatively traced back to a ligand rearrangement in the presence of AlEt₃. After a fast initial phase, a pronounced ‘kink’ in the ethylene‐uptake curve is observed, followed by a slow, almost linear, further increase of the total ethylene consumption. The catalyst composition, in particular the ligand/chromium and the cocatalyst/chromium molar ratio, has a strong impact on the catalytic performance of the trimerization of ethylene.     

Fundamental Problems in the Unification of Physics

We discuss the following problems, plaguing the present search for the “final theory”: (1) How to find a mathematical structure rich enough to be suitably approximated by the mathematical structures of general relativity and quantum mechanics? (2) How to reconcile nonlocal phenomena of quantum mechanics with time honored causality and reality postulates? (3) Does the collapse of the wave function contain some hints concerning the future quantum gravity theory? (4) It seems that the final theory cannot avoid the problem of dynamics, and consequently the problem of time. What kind of time, if this theory is supposed to be background free? (5) Will the dynamics of the “final theory” be probabilistic? Quantum probability exhibits some essential differences as compared with classical probability; are they but variations of some more general probabilistic measure theory? (6) Do we need a radically new interpretation of quantum mechanics, or rather an entirely new theory of which the present quantum mechanics is an approximation? (7) If the final theory is to be background free, it should provide a mechanism of space-time generation. Should we try to explain not only the generation of space-time, but also the generation of its material content? (8) As far as the existence of the initial singularity is concerned, one usually expects either “yes” or “not” answers from the final theory. However, if the mathematical structure of the future theory is supposed to be truly more general that the mathematical structures of the present general relativity and quantum mechanics, is a “third answer“ possible? Could this third answer be related to the probabilistic character of the final theory? We discuss these questions in the framework of a working model unifying gravity and quanta. The analysis reveals unexpected aspects of these rather wildly discussed issues.     

A Fast and Efficient Track to Allosteric Modulators of Muscarinic Receptors: Microwave-Assisted Syntheses

By using microwave irradiation bisammonium-and bispyridinium-type allosteric modulators of muscarinic receptors can be obtained fast and efficiently.     

Covalent Protein Labeling by Enzymatic Phosphocholination

We present a new protein labeling method based on the covalent enzymatic phosphocholination of a specific octapeptide amino acid sequence in intact proteins. The bacterial enzyme AnkX from Legionella pneumophila has been established to transfer functional phosphocholine moieties from synthetically produced CDP‐choline derivatives to N‐termini, C‐termini, and internal loop regions in proteins of interest. Furthermore, the covalent modification can be hydrolytically removed by the action of the Legionella enzyme Lem3. Only a short peptide sequence (eight amino acids) is required for efficient protein labeling and a small linker group (PEG‐phosphocholine) is introduced to attach the conjugated cargo.