The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes

By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A₂L₃ complexes (A represents anion, here orthophosphate PO₄^3?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes.     

Spectral estimates for saddle point matrices arising in weak constraint four‐dimensional variational data assimilation

We consider the large sparse symmetric linear systems of equations that arise in the solution of weak constraint four‐dimensional variational data assimilation, a method of high interest for numerical weather prediction. These systems can be written as saddle point systems with a 3 × 3 block structure but block eliminations can be performed to reduce them to saddle point systems with a 2 × 2 block structure, or further to symmetric positive definite systems. In this article, we analyse how sensitive the spectra of these matrices are to the number of observations of the underlying dynamical system. We also obtain bounds on the eigenvalues of the matrices. Numerical experiments are used to confirm the theoretical analysis and bounds.     

Electroactive conducting polymers for corrosion control

There is an intensive effort underway to develop new corrosion control coatings for structural metals. In part, this effort has been motivated by the desire to replace chromium(VI)-containing coatings currently used for corrosion control of iron and aluminum alloys. Cr(VI) has been shown to be hazardous to the environmental and to human health, and its use in many countries will be sharply curtailed in the coming years. Electroactive conducting polymers (ECPs) represent a class of interesting materials currently being explored for use in corrosion control coating systems, possibly as a replacement for Cr(VI)-based coatings. The electroactivity and the electronic conductivity (or semiconductivity) of ECPs set them apart from traditional organic coatings. As with chromate, interesting and potentially beneficial interactions of ECPs with active metal alloys such as steel and aluminum are anticipated, with concomitant alteration of their corrosion behavior. A review of this active research area will be presented in two parts. Here in Part 1, a general introduction to the topic of corrosion control by ECPs will be presented, including an overview of corrosion and its control by traditional methods, an introduction to ECPs and their properties, and a discussion of the processing issues surrounding the use of ECPs as coatings. Part 1 also includes a review of the literature on the use of ECPs as coatings (or components of coatings) on non-ferrous active metals, principally aluminum and aluminum alloys, although some work on zinc, copper, silver, titanium and silicon will also be described. In Part 2 of this review (to be published in the next issue of this journal), the rather extensive literature on the use of ECPs for the corrosion control of ferrous alloys (steels) will be reviewed. Electronic Publication     

Microwave-accelerated Claisen rearrangements of allyl tetronates and tetramates

[3,3]-Sigmatropic rearrangements of allyl tetronates and allyl tetramates to give 3-allyltetronic or -tetramic acids, respectively, proceed within 20-60 min under microwave irradiation (300 W, 130-190 °C). Consecutive (homo)sigmatropic [1,5] H-shifts such as oxa-ene reactions are promoted less effectively, which allows the isolation of Claisen intermediates of sigmatropic domino sequences, in contrast to conventional heating.     

Electron spin lifetimes in Hg0.78Cd0.22 Te and InSb

We have made direct pump–probe measurements of spin lifetimes in long wavelength narrow-gap semiconductors at wavelengths between 4 and 10 μm and from 4 to 300 K. In particular, we measure remarkably long spin lifetimes, τ_s300 ps, even at 300 K for epilayers of degenerate n-type InSb. In this material the mobility is approximately constant between 77 and 300 K, and we find that τ_s is approximately constant in this temperature range. In order to determine the dominant spin relaxation mechanism we have investigated the temperature dependence of τ_s in non-degenerate lightly n-type Hg_0.78Cd_0.22Te of approximately the same band gap as InSb, and find that τ_s varies from 356 ps at 150 K to 24 ps at 300 K. Our results, both in magnitude and temperature dependence of τ_s, imply that the Elliott–Yafet model dominates in these materials.     

An improved synthesis of isonitrosoacetanilides

A novel two-step synthesis of isonitrosoacetanilides [2-(hydroxyimino)-N-phenylacetamides] has been developed, involving the initial acylation of aniline derivatives with 2,2-diacetoxyacetyl chloride, followed by reaction with hydroxylamine hydrochloride. The method works equally well with a variety of different aniline derivatives, including those with poor aqueous solubility and those containing electron rich ortho-substituents, neither of which react well under traditional conditions.