Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes

A first example of an Et₂Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.     

Connectedness of the Isospectral Manifold for One-Dimensional Half-Line Schrödinger Operators

Journal of Statistical Physics - Let V 0be a real-valued function on [0,∞) and V∈L 1([0,R]) for all R&;gt;0 so that H(V 0)=? $\frac{{d^2 }}{{dx^2 }}$ +V 0in L 2([0,∞))...     

A historical note on the entropy principle of Müller and Liu

Received July 12, 2001 / Published online February 28, 2002     

The Mössbauer effect and collective motions in glass-forming liquids and polymeric networks

Glass-forming liquids, synthetic polymers and biopolymers share essential properties. Dynamic processes in these complex systems are characterized by cooperative motions with wide distributions of time scales, which manifest themselves in broad quasielastic lines in the Mössbauer spectrum. In this article, the application of the Mössbauer effect to the study of structural dynamics in complex systems is discussed.     

Microbial Baeyer-Villiger Oxidation of Ketones by Cyclohexanone and Cyclopentanone Monooxygenase – A Computational Rational for Biocatalyst Performance

Summary. Recombinant Escherichia coli overexpressing Pseudomonas sp. NCIMB 9872 cyclopentanone monooxygenase (CPMO, EC 1.14.13.16) and Acinetobacter sp. NCIMB 9871 cyclohexanone monooxygenase (CHMO, EC 1.14.13.22) have been utilized in whole-cell Baeyer-Villiger biotransformations of prochiral bicycloketones. A significant difference in substrate acceptance and stereoselectivity was observed for bicyclo[3.3.0] and bicyclo[4.3.0] substrates. A plausible mechanism of these transformations was established by means of high level DFT/B3LYP calculations suggesting an essential difference in electronic requirements for a successful enzymatic conversion, which was similarly encountered in recombinant whole-cell mediated biooxidations. Some of the lactones produced in the biocatalytic Baeyer-Villiger oxidation represent key intermediates for the synthesis of indole alkaloids.     

The Arrow of Time in the Equations of Motion

It is argued that time's arrow is present in all equations of motion. But it is absent in the point particle approximations commonly made. In particular, the Lorentz-Abraham-Dirac equation is time-reversal invariant only because it approximates the charged particle by a point. But since classical electrodynamics is valid only for finite size particles, the equations of motion for particles of finite size must be considered. Those equations are indeed found to lack time-reversal invariance, thus ensuring an arrow of time. Similarly, more careful considerations of the equations of motion for gravitational interactions also show an arrow of time. The existence of arrows of time in quantum dynamics is also emphasized.