Nitrone [2]rotaxanes: Simultaneous chemical protection and electrochemical activation of a functional group

We report on the use of the hydrogen bond accepting properties of neutral nitrone moieties to prepare benzylic-amide-macrocycle-containing [2]rotaxanes in yields as high as 70 %. X-Ray crystallography shows the presence of up to four intercomponent hydrogen bonds between the amide groups of the macrocycle and the two nitrone groups of the thread. Dynamic 1H NMR studies of the rates of macrocycle pirouetting in nonpolar solutions indicate that amide-nitrone hydrogen bonds are particularly strong, ~1.3 and ~0.2 kcal mol-1 stronger than similar amide-ester and amide-amide interactions, respectively. In addition to polarizing the N-O bond through hydrogen bonding, the rotaxane structure affects the chemistry of the nitrone groups in two significant ways: The intercomponent hydrogen bonding activates the nitrone groups to electrochemical reduction, a one electron reduction of the rotaxane being stablized by a remarkable 400 mV (8.1 kcal mol-1) with respect to the same process in the thread; encapsulation, however, protects the same functional groups from chemical reduction with an external reagent (and slows down electron transfer to and from the electroactive groups in cyclicvoltammetry experiments). Mechanical interlocking with a hydrogen bonding molecular sheath thus provides a route to an encapsulated polarized functional group and radical anions of significant kinetic and thermodynamic stability.

The adoption of advanced quality practices and its impact on manufacturers

Presently, the manufacturing sector faces unprecedented levels of competition in both the domestic and international markets. This competition is mainly as a result of rapidly expanding international trade, gradual removal of protection, substantial reforms in labour markets and industrial relations, rapid technological changes and discerning customers. Intense global competition requires manufacturers to deliver products with higher quality in a shorter time. Simultaneously, owing to new technological innovations, the complexity of the products is increasing. In Australia, the impact of this intense competition and structural changes appear to be having negative effects on the manufacturing sector. This paper discusses the quality and reliability (Q & R) practices and associated drawbacks of Australian manufacturers and presents the findings of an investigation of the challenges Australian manufacturers are currently facing. The results reported in the paper are based on the data collected from a survey using the standard questionnaire. The study was driven by a conceptual model, which relates advanced quality practices to manufacturing performance and manufacturing difficulties.Evidence indicates that Q & R is the main competitive factor for Australian manufacturers. Design capability and on time delivery (OTD) came second. Results show that Australian manufacturers in general are facing some manufacturing difficulties. The relationship between advanced quality practices and company performance and manufacturing difficulties are explored. It is found that the companies who have more emphasis on advanced quality practices have fewer problems in manufacturing practices. Moreover, companies who have actively implemented the advanced quality practices have managed to improve the quality of the product continuously. The results validate the proposed hypothesis and lend credence to current thinking that improvement in Q & R is a vital tool for competitive advantage.