Prasad L. Polavarapu (Ed.): Chiral analysis: advances in spectroscopy,chromatography, and emerging methods, 2nd ed.

Analytical and Bioanalytical Chemistry -     

On combinatorial and projective geometry

Cross ratios constitute an important tool in classical projective geometry. Using the theory of Tutte groups as discussed in [6] it will be shown in this note that the concept of cross ratios extends naturally to combinatorial geometries or matroids. From a thorough study of these cross ratios which, among other observations, includes a new matroid theoretic version and proof of the Pappos theorem, it will be deduced that for any projective space M= _n (K) of dimension n2 of M over some skewfield K the inner Tutte group is isomorphic to the commutator factor group K ^*/[K ^*, K ^*] of K ^*K{0}. This shows not only that in case M= _n (K) our matroidal cross ratios are nothing but the classical ones. It can also be used to correlate orientations of the matroid M= _n (K) with the orderings of K. And it implies that Dieudonné's (non-commutative) determinants which, by Dieudonné's definition, take their values in K ^*/[K ^*, K ^*] as well, can be viewed as a special case of a determinant construction which works for just every combinatorial geometry.Research supported by the DFG (Deutsche Forschungsgemeinschaft).     

On the Nature of the 7-Norbornadienyllithiums. Preliminary Communication

Lithium reductions of 7-chloronorbornadiene and of bis(7-norbornadienyl)mercury both provide (C₇H₇)₂Li₂ ( 5a ). This product is accompanied by C₇H₇Li₂Cl ( 5c ) in the first case, and by C₇H₇Li ( 5b ) in the second. The theoretically anticipated properties of all three organolithiums are apparent in the consistent C_s symmetry of their hydrocarbon ligands, their protolytic destruction by 12-crown-4, and their significant J(C(7), Li) ( 5a , 7.6; 5b , 16.0; 5c 8.9 Hz).     

One-step cleanup for PAH residue analysis in plant matrices using size-exclusion chromatography

A new one-step cleanup procedure, based on size-exclusion chromatography (SEC), usable for the extracts from accelerated solvent extraction (ASE), Soxhlet extraction, or ultrasonic extraction (USE), is described. The method is suitable for the determination of polycyclic aromatic hydrocarbons (PAHs), especially from very complicated plant matrices (e.g. pine needles, deciduous leaves, mosses). The main improvement compared with previous conventional procedures is that analyte peaks barely overlap with matrix peaks in the chromatograms and that it is a very rapid and simple one-step procedure with clearly improved analytical performance. Essential advantages of this SEC procedure are the sharper GC-MS chromatograms for the PAH fraction at retention times between 9.2 and 12.0 min, distinctly separated substance peaks resulting in better analysis, shorter running times, and lower solvent consumption.     

The electric field gradient at111Cd in vanadium oxides

The electric field gradient (efg) of¹¹¹Cd in polycrystalline V₂O₅ was studied using perturbed angular correlation (PAC) spectroscopy, with the¹¹¹In activity ion-implanted at 400 keV. Between the individual steps of an isochronal annealing program, a distinct efg (v _Q 1=88.1(3) MHz, ₁=0.62(2)) was recorded the contribution of which increased with annealing temperature up to 74% at 870 K. Corresponding X-ray analysis of inactive V₂O₅ samples, which underwent the same annealing treatment, proved that the sample always stayed as V₂O₅. Since V₂O₅ has only one equivalent cation site, it is concluded that this efg belongs to¹¹¹Cd at this site. Oxidation of a vanadium foil atT=675 and 800 K at =200 mbar also yielded this efg. From PAC measurements in VO₂, two well-defined efg's were found above and below the metal-semiconductor transition at 340 K, which are tentatively attributed to the monoclinic and the tetragonal phase.Supported by Deutsche Forschungsgemeinschaft and DAAD.On leave from the University of Durban-Westville, South Africa.     

Soliton experiments in stimulated Raman scattering

Experimental observations of solitons in stimulated Raman scattering are reported. Soliton formation resulted from the introduction of a phase shift in the incident Stokes beam as predicted by theory. Pulse sharpening and retardation on propagation in the Raman medium have been observed along with amplitude diminution. The first two features were predicted and the third was not. Spontaneous soliton formation has been observed in the absense of any amplitude modulation or apparent phase shift in the optical fields, indicating that additional sets of initial conditions may result in soliton formation.Work performed under the auspices of the U.S. Department of Energy.     

Configuration interaction (CI): Approximate inclusion of fourfold and threefold excitations,an application of knowledge engineering

It is shown that even the CPMET approximation for the contributions of fourfold excitations can be replaced by a more sophisticated method. Furthermore, an approximation is presented for the contributions of threefold excitations which are neglected in CPMET . Finally, it is described how the advantages of different CEPA methods can be united in a single CEPA scheme (called CEPA -U). The various approximations are discussed in terms of Slater determinants, and it is shown how the relatively large amount of details can be handled with the help of computer programs, i.e., how knowledge engineering can be successfully applied here.     

Polyamine-based anion receptors: Extraction and structural studies

In the discussion that follows some of the more recent progress in the area of anion binding by synthetic polyamine receptors is presented, with emphasis given to work undertaken by the authors’ groups. A continuing theme in these studies has been the relationship between receptor structure and its anion extraction properties.Systematic solvent extraction and structural studies for halide and perrhenate complexes with polyamines of tripodal, macrocyclic and macrobicyclic architecture that contain both aromatic moieties and four to eight amine functions have been performed in order to derive relevant structure-binding/extractability relationships. The results demonstrate that the binding and extraction behaviour of the polyamines towards halides and perrhenate is a complex function of their structural features, degree of protonation and lipophilic properties. The extraction is characterized by the preferred formation of mono- and diprotonated amine species in the organic phase. X-ray structure studies of iodide and perrhenate complexes with open-chain tetraamino derivatives and octaamino cryptands in different protonation states lead to the conclusion that in the first case only limited chelation of the anion occurs and in the second only highly protonated species are able to encapsulate the anion. The structural patterns observed are strongly influenced by the presence of water molecules in the crystals.