Carbon Participation in the Solvolysis of 6-exo-substituted 2-exo- and 2-endo-Norbornyl p-Toluenesulfonates. Norbornanes part 5

The solvolysis rates and products of the 6-exo-substituted 2-exo- 1a - 1u , and 2-endo-norbornyl p-toluenesulfonates 2a - 2u , have been determined. In general, the rate constants for 1 and 2 (log k) correlate well with the inductive constants σ of the substitutents at C(6); however, their sensitivity to σ is much larger in the 2-exo-series 1 than in the 2-endo-series 2 . This differential transmission of polar effects is the cause of decreasing 2-exo/2-endo rate ratios from 2388 for R = t-C₄H₉ to 0.37 for R = Br, i. e. with increasing electron attraction by the substituent. The high sensitivity of the rate constants for the 2-exo-p-toluenesulfonates 1 to σ indicates an unusually strong inductive interaction between C(6) and the incipient cationic center at C(2). This interaction is ascribed to the participation of the pentacoordinate C(6)-atom, i. e. to 1,3-bridging, a consequence of steric hindrance of nucleophilic solvent participation in norbornanes. Donor substituents enhance 1,3-bridging, lead to faster reactions and to the formation of 2-exo substitution products. Conversely, acceptor substituents reduce 1,3-bridging, decrease rates and facilitate the formation of 2-endo substitution products. Graded 1,3-bridging is discussed in the light of Winstein's nonclassical ion concept.     

Eisen(III)-rhodanidpapier als analytisches Reagens bei Luftuntersuchungen

Zusammenfassung Mit Hilfe von Reagenspapierstreifen, die mit Eisen(III)-rhodanid imprÄgniert sind, lassen sich alle in der Luft gelegentlich vorkommenden, alkalisch reagierenden Gase oder DÄmpfe (Ammoniak, Amine, Äthylenoxyd) nachweisen. Das dunkelrotbraune Reagenspapier wird hierbei entfÄrbt. Das Ausma\ der EntfÄrbung folgt stöchiometrischen Gesetzen. Der Grad der EntfÄrbung lÄ\t sich daher quantitativ auswerten. Eine untere und obere Nachweisgrenze gibt es bei diesem Verfahren theoretisch überhaupt nicht. Bei der vorgeschlagenen Ausführungsmethode, die eine Absaugung von Luftmengen bis zu 1 Liter vorsieht, liegt die untere Nachweisgrenze — in AnhÄngigkeit von dem Molekulargewicht des gefundenen Stoffes — z. B. bei 0,07 g NH₃ je Liter Luft (=0,07 mg/m₃) oder bei 0,25 g Trimethylamin/1 Liter (=0,25 mg/m³). Die praktische Begrenzung nach oben liegt dort, wo sich andere bekannte Bestimmungsmethoden mit höherem Genauigkeitsgrad anbieten.Die Herstellung eines in reiner Luft auch bei Licht und Zimmertemperatur lÄngere Zeit haltbaren Reagenspapiers wird beschrieben. Die praktische Anwendbarkeit des ER-Papiers liegt vor allem bei Luftuntersuchungen im Zusammenhang mit den Exhalationen und Emanationen von Fischmehlfabriken.     

Molecular chaperones--cellular machines for protein folding

Proteins are linear polymers synthesized by ribosomes from activated amino acids. The product of this biosynthetic process is a polypeptide chain, which has to adopt the unique three-dimensional structure required for its function in the cell. In 1972, Christian Anfinsen was awarded the Nobel Prize for Chemistry for showing that this folding process is autonomous in that it does not require any additional factors or input of energy. Based on in vitro experiments with purified proteins, it was suggested that the correct three-dimensional structure can form spontaneously in vivo once the newly synthesized protein leaves the ribosome. Furthermore, proteins were assumed to maintain their native conformation until they were degraded by specific enzymes. In the last decade this view of cellular protein folding has changed considerably. It has become clear that a complicated and sophisticated machinery of proteins exists which assists protein folding and allows the functional state of proteins to be maintained under conditions in which they would normally unfold and aggregate. These proteins are collectively called molecular chaperones, because, like their human counterparts, they prevent unwanted interactions between their immature clients. In this review, we discuss the principal features of this peculiar class of proteins, their structure-function relationships, and the underlying molecular mechanisms.     

Instability of nonlinear bound states

We establish a sharp instability theorem for the bound states of lowest energy of the nonlinear Klein-Gordon equation,u _tt–u+f(u)=0, and the nonlinear Schrödinger equation, –iu _t–u+f(u)=0.Supported in part by NSF Grants MCS 81-21487 and MCS 82-01599     

A Simple proof of the generalized electrostatic Israel theorem

A simple proof of a generalization of the theorem of Israel concerning the uniqueness of the Reissner-Nordström black holes is presented. The present method is also applied to show, in the bosonic sector ofN=4-supergravity, the uniqueness of a static black hole solution found by Gibbons.Work supported by Fonds zur Förderung der wissenschaftlichen Forschung in Österreich, Project No. 4961.     

Gravitational field strength and generalized Komar integral

We define a gravitational field strength in theories of the Einstein-Cartan type admitting a Killing vector. This field strength is a second rank, antisymmetric, divergence-free tensor, whose (Komar) integral over a closed 2-surface gives a physically meaningful quantity. We find conditions on the Lagrange density of the theory which ensure the existence of such a tensor, and show that they are satisfied forN=2-supergravity and for a special case of the bosonic sector ofN=4-supergravity. We discuss a possible application of the generalized Komar integral in the theory of stationary black holes. We also consider the field strength problem in Kaluza-Klein theory, where the application to black holes is particularly interesting.     

Synthesis and evaluation of stereopure α-trifluoromethyl-malic hydroxamates as inhibitors of matrix metalloproteinases

The total synthesis of trifluoromethyl (Tfm) analogs of known nanomolar matrix metalloproteinases (MMPs) inhibitors has been performed. The synthetic protocol is based on a moderately stereoselective aldol reaction of trifluoropyruvate with an N-acyl-oxazolidin-2-thione for the construction of the core α-Tfm-malic unit. Both the diastereomeric forms of the target α-Tfm-malic hydroxamates showed micromolar inhibitory potency toward MMP-2 and 9, with a substantial drop with respect to the parent unfluorinated compounds.