Synthesis of muscothiazoles A and B: Critical role of methyl group substitution in RCM-based syntheses of macrocycles

[reaction: see text] Muscothiazoles A (2b) and B (2c) have been prepared by two approaches that differ in the order of assembly of the rings. Comparative studies show that substitution of the carbon chains in substrate 5 or 12 (respective precursors to 13-membered and 14-membered rings by RCM), even by a single methyl group, can have a profound effect on increasing the efficiency of the macrocyclization.     

Erratum to: Tensionless contact of a finite circular plate

In the electronic version of the original article, the issue number shown in the header of the article opening page was wrong. It should be Issue 5 as in Acta Mechanica Sinica (2012) 28(5): 1374-1381.     

O- radical ions on MgO: a tool for a structural description of the surface

The present contribution aims to show that detailed information on structure and location of surface defective sites (surface vacancies, low co-ordination sites) can be obtained by combining data on the chemical reactivity of polycrystalline surfaces and EPR data. The use of nitrous oxide for bleaching trapped electron centres at the surface of MgO produces a remarkable variety of O^- species, which differ in their values of the energy splitting (δE) term between the p_z and the other two p orbitals of the radical ion. This indicates the existence of a corresponding variety of surface traps having different structural features.     

Multilayer hydrous oxide growth on copper in base and its correlation with previously reported electrocatalytic data for this electrode system

A repetitive potential cycling procedure was used to produce a specific multilayer hydrous oxide film on copper in base at 60 °C. Such a deposit undergoes reduction in a quasi-reversible manner at ca. −0.1 V (RHE), i.e. at a potential that is unrelated to Pourbaix data for copper but, as demonstrated previously, is of major significance with regard to the electrocatalytic behaviour of this electrode system. In accordance with the incipient hydrous oxide/adatom mediator model of electrocatalysis, an active surface state of the metal (Cu*) is assumed to be involved both in electrocatalysis and as a primary product in the hydrous oxide reduction reaction. While the latter process occurs very rapidly at −0.1 V, it is not usually reversible as it is accompanied by subsequent rapid loss of the active state of the metal. The same general approach was used previously to explain the hydrous oxide and electrocatalytic behaviour of a range of noble metals. Received: 28 August 1999 / Accepted: 11 November 1999     

Synthesis,self‐assembly and adsorption of PEO–PLA block copolymers onto colloidal polystyrene

A series of amphiphilic block copolymers composed of poly(ethylene oxide) and poly(lactide) were synthesized and their solution properties studied using static and dynamic light scattering. These materials self‐assemble in aqueous media with the hydrodynamic radius increasing with increasing hydrophobic fraction in the copolymer. To ascertain the potential for use of these materials as degradable coatings in delivery applications, block copolymers of varying compositions were adsorbed onto a series of colloidal polystyrene particles with varying radii, and the thickness of the adsorbed layer was determined from changes in the hydrodynamic size. The adlayer thicknesses ranged from 3 to 14 nm with varying block copolymer compositions, and colloid radii. The trends fit well with theoretical models for adlayer thickness, with the exception of the smallest colloids. In these systems, we propose that the colloids may become encapsulated into the block copolymer assembly. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 244–252, 2008     

Atomgewichte

Ohne Zusammenfassung     

Exchange enhanced sensitivity gain for solvent-exchangeable protons in 2D 1H-15N heteronuclear correlation spectra acquired with band-selective pulses

Conformational or chemical exchange can cause significant sensitivity loss in NMR spectroscopy through resonance broadening for nuclear spins involved in these processes. While this effect may sometimes be alleviated by manipulating experimental conditions such as temperature, pH, and buffers, conditions optimal for all resonances are not always achievable. As a consequence, any means of recovering or minimizing this exchange-induced sensitivity loss is potentially of significant value in regaining information otherwise lost. We report the experimental observation of significant sensitivity gain for nuclear spins undergoing chemical exchange with solvent (water) at exchange rates ca 1-10 s(-1) in (1)H-(15)N correlation spectra of proteins acquired with band-selective pulses (the SOFAST-HMQC sequence).