C, N CPMAS NMR and GIAO DFT calculations of stereoisomeric oxindole alkaloids from Cat's Claw (Uncaria tomentosa)

Oxindole alkaloids, isolated from the bark of Uncaria tomentosa [Willd. ex Schult.] Rubiaceae, are considered to be responsible for the biological activity of this herb. Five pentacyclic and two tetracyclic alkaloids were studied by solid-state NMR and theoretical GIAO DFT methods. The ¹³C and ¹⁵N CPMAS NMR spectra were recorded for mitraphylline, isomitraphylline, pteropodine (uncarine C), isopteropodine (uncarine E), speciophylline (uncarine D), rhynchophylline and isorhynchophylline. Theoretical GIAO DFT calculations of shielding constants provide arguments for identification of asymmetric centers and proper assignment of NMR spectra. These alkaloids are 7R/7S and 20R/20S stereoisomeric pairs. Based on the ¹³C CP MAS chemical shifts the 7S alkaloids (δ C3 70–71 ppm) can be easily and conveniently distinguished from 7R (δC3 74.5–74.9 ppm), also 20R (δC20 41.3–41.7 ppm) from the 20S (δC20 36.3–38.3 ppm). The epiallo-type isomer (3R, 20S) of speciophylline is characterized by a larger ¹⁵N MAS chemical shift of N4 (64.6 ppm) than the allo-type (3S, 20S) of isopteropodine (δN4 53.3 ppm). ¹⁵N MAS chemical shifts of N1–H in pentacyclic alkaloids are within 131.9–140.4 ppm.     

Piggyback dualities revisited

In natural duality theory, the piggybacking technique is a valuable tool for constructing dualities. As originally devised by Davey and Werner, and extended by Davey and Priestley, it can be applied to finitely generated quasivarieties of algebras having term-reducts in a quasivariety for which a well-behaved natural duality is already available. This paper presents a comprehensive study of the method in a much wider setting: piggyback duality theorems are obtained for suitable prevarieties of structures. For the first time, and within this extended framework, piggybacking is used to derive theorems giving criteria for establishing strong dualities and two-forone dualities. The general theorems specialise in particular to the familiar situation in which we piggyback on Priestley duality for distributive lattices or Hofmann–Mislove– Stralka duality for semilattices, and many well-known dualities are thereby subsumed. A selection of new dualities is also presented.     

Simulation of phase separation in alcohol/water mixtures using two-body force field and standard molecular dynamics

Standard molecular dynamics simulations have been carried out on pure alcohols and alcohol/water mixtures. A simple atom-atom force field consisting of Lennard-Jones potentials plus coulombic terms over atomic point charges, but without explicit polarization terms, has been specifically fitted to reproduce several experimental properties of the pure alcohols, and has been used for mixtures by developing combination rules with the TIP3P water model. Densities, enthalpies of vaporization, radial distribution functions, self-diffusion coefficients, and rotational correlation functions of the pure alcohols are well reproduced and compare favorably with those from more sophisticated force fields. Some key aspects of the phase behaviour are correctly reproduced by the molecular dynamics simulation, showing a distinct demixing process for the n-butanol/water mixture as opposed to the stability of the t-butanol/water mixtures. The results demonstrate the ability of a molecular dynamics simulation, even in its standard form and with easily accessible time ranges, but with a carefully optimized force field, to simulate and, to a certain extent, predict the properties of binary mixtures.     

Laser performance studies of para-(phenylene-ethynylene) polymers in organic solvents

The lasing performance of the polymers poly(2,5-dioctadecyloxy-paraphenylene-ethynylene-co-2,5-thienyl) (OPT) and poly(2,5-dioctadecyloxy-paraphenylene-ethynylene-co-2,5-pyridinyl) (OPP) in organic solvents was studied. A two-mirror resonator was transversally pumped using single pulses of the second harmonic of a mode-locked ruby laser. OPT in tetrahydrofuran lased in the region from 480 nm to 525nm and OPP in tetrahydrofuran showed laser action in the region from 460 nm to 490nm. The polymer solutions are characterized by absorption and fluorescence spectroscopic analysis. Effective stimulated emission cross-sections are reported. High excited-state absorption cross-sections and residual ground-state absorption reduce the lasing efficiency. This revised version was published online in November 2006 with corrections to the Cover Date.     

Applications of Mössbauer spectroscopy in the geochemistry of sedimentary rocks

A set of pure iron-rich minerals characteristic of common fine-grained sedimentary rocks has been prepared and their Mössbauer spectra obtained. These include pyrite, carbonates and silicates. Six marine mudrocks were then chosen from a large set for which complete chemical data were available. It proved possible to reproduce mudrock spectra by addition of the pure mineral spectra in proportions indicated by the chemical analyses. Unfortunately, however, overlap of Fe(III) in dioctahedral silicates with Fe(II) in pyrite prevents reliable deconvolution of mudrock spectra to obtain quantitative estimates of component concentrations. Useful information about Fe(II) in other minerals can still be obtained. Mössbauer spectroscopy would appear to have great promise for the study of early reactions in non-marine sediments which are usually low in sulphur. Mineral products are either X-ray amorphous or extremely fine-grained mixtures and very difficult to study by other means.     

Optimal natural dualities. II: General theory

A general theory of optimal natural dualities is presented, built on the test algebra technique introduced in an earlier paper. Given that a set of finitary algebraic relations yields a duality on a class of algebras , those subsets of which yield optimal dualities are characterised. Further, the manner in which the relations in are constructed from those in is revealed in the important special case that generates a congruence-distributive variety and is such that each of its subalgebras is subdirectly irreducible. These results are obtained by studying a certain algebraic closure operator, called entailment, definable on any set of algebraic relations on . Applied, by way of illustration, to the variety of Kleene algebras and to the proper subvarieties of pseudocomplemented distributive lattices, the theory improves upon and illuminates previous results.