Investigation of Cr(III) hydrolytic polymerisation products by capillary electrophoresis-inductively coupled plasma-mass spectrometry

The development of a new method for the determination of Cr(III) hydrolytic polymerisation products using capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) is described. The results indicate that CE-ICP-MS can be used to separate and detect monomeric and polymeric Cr(III) species. The various species migrate through the capillary at a rate proportional to their equilibrium distribution, which is dictated by the solution pH, metal ion concentration and ageing period. In general, the data suggest that the relative mobility follows the order trimer>dimer>monomer. The experimentally determined speciation shows a good qualitative agreement with that described in the literature. Independent confirmation of the presence of polymeric Cr(III) species was performed by ionspray mass spectrometry.     

Improving the stereoselectivity of bakers' yeast reductions by genetic engineering

[formula: see text] The stereoselectivities of bakers' yeast catalyzed reductions of beta-keto esters can be manipulated by genetic design. Strains in which two major beta-keto ester reductases are either knocked out or overexpressed have been constructed. The former approach results in whole cell biocatalysts with reversed stereoselectivity from unmodified bakers' yeast while the latter shows useful improvements in stereoselectivity. These results indicate that the "designer yeast" approach can provide useful biocatalysts for these transformations.     

Regular Subgraphs in Graphs and Rooted Graphs and Definability in Monadic Second - Order Logic

We investigate the definability in monadic ∑₁¹ and monadic Π₁¹ of the problems REG_k, of whether there is a regular subgraph of degree k in some given graph, and XREG_k, of whether, for a given rooted graph, there is a regular subgraph of degree k in which the root has degree k, and their restrictions to graphs in which every vertex has degree at most k, namely REG_k^k and XREG_k^k, respectively, for k ≥ 2 (all our graphs are undirected). Our motivation partly stems from the fact (which we prove here) that REG_k^k and XREG_k^k are logspace equivalent to CONN and REACH, respectively, for k ≥ 3, where CONN is the problem of whether a given graph is connected and REACH is the problem of whether a given graph has a path joining two given vertices. We use monadic first - order reductions, monadic ∑₁¹ games and a recent technique due to Fagin, Stockmeyer and Vardi to almost completely classify whether these problems are definable in monadic ∑₁¹ and monadic Π₁¹, and we compare the definability of these problems (in monadic ∑₁¹ and monadic Π₁¹ with their computational complexity (which varies from solvable using logspace to NP - complete).     

Reactions involving fluoride ion. Part 40. Amines as initiators of fluoride ion catalysed reactions

Tetrakis(dimethylamino)ethene (TDAE) and trimethylamine react with anhydrous unsaturated fluorocarbons to produce, ‘in situ’, powerful fluoride- ion sources. These are used to initiate carbon- carbon bond forming reactions eg. oligomerisation and polyfluoroalkylation, and many of these reactions occur efficiently in the absence of a solvent.     

Mathematics for young people: The royal institution masterclasses

The Mathematical Intelligencer - We expected a fair number of participants to drop out as the course progressed. Indeed, we had raised the numbers to 48 anticipating this. In fact the average level...     

A procedure for obtaining lower bounds for ground state energies of atoms and molecules

Using Löwdin's partition method we have re-derived the D. Weinstein lower bound, E > H ₁₁ - . By the same method, plus the assumption that the calculated first excited state energy is lower than a certain weighted average of approximate energies of all the excited states, we have derived a moderately better lower bound.     

A Mössbauer effect study of Y(57Fe:Mn)12

The intermetallic compound, YMn₁₂, doped with 0.5at.%⁵⁷Fe has been investigated using the⁵⁷Fe Mössbauer resonance. The data show that the Fe impurities occupy preferentially the f-site at the expense of the i- and j-sites. Whereas the i- and j-sites are expected to carry identical local magnetic moments in the ordered state, low temperature hyperfine fields of 50.08(±0.05)T and 2.90(±0.03)T are measured for the i- and j-sites respectively. It is proposed that large transferred hyperfine fields are responsible for this disparity.