Estimates of Stark broadening of oxygen ion lines

Recent measurements of spectral line widths for singly- and doubly-ionized oxygen atoms, are compared with the corresponding values predicted by the semi-empirical method of Griem. On the basis of these results, as well as a similar comparison for singly- and doubly-ionized nitrogen atoms in a recent paper, we propose some “experimental” values of the threshold Gaunt factors for these ions.     

Improvements in the clinical utility of calculated T2 images of the human brain

Magnetic Resonance Imaging (MRI) affords a considerable improvement in image contrast over other methods by virtue of the intrinsic NMR parameters spin density, T1, and T2. However, the clinical utility of routine quantification of these parameters is currently unknown. Calculated T2 images might afford additional disease specific information provided the calculation algorithm generates accurate T2 values. In this study, calculated T2 images of a MnCl2 phantom (spanning a T2 range of interest of 45.7 ms to 346.6 ms at 6 MHz) were generated utilizing a variety of calculation algorithms based upon a data set of 32 sequential spin-echo (SE) images. In general, when utilizing only the earliest sequential SE after the 90 degree pulse for the T2 calculation, the greater the number of SE used in the calculation algorithm, regardless of how they were averaged, the more accurate and less noisy was the calculated image. When only limited numbers of SE were used in the calculation algorithm, accuracy and noise varied with the choice of TE suggesting that there may be optimal timings for TE for a particular T2 range of interest. Forty-two calculated T2 head images of normal subjects, based upon data sets of 16 sequential SE, were evaluated for the T2 values of normal brain. These were compared to T2 images calculated via 7 different algorithms based upon 16 SE data sets from two patients with CNS pathology. An optimal algorithm was identified in which 16 SE Carr-Purcell-Meiboom-Gill (CPMG) were averaged into two images for the T2 calculation. With this algorithm, calculated images could be generated efficiently which were accurate and relatively noise free. The availability of such images maximized whatever disease specificity, and thus clinical utility, T2 information affords.     

Quotients of group algebrae in the calculation of intermediate ligand field matrix elements

The structure of the classes of symmetry elements excluded during the subduction of the representations of SU(2) onto the finite group 0* is shown to quantitatively define the relationship of the coupling algebrae of these two groups. This relationship is formalized as a quotient algebra. This quotient algebra is realized as 3-like symbols which exist whether or not the quotient can be defined as a group. These symbols distribute the value of a reduced matrix element of SU(2) onto the subduced reduced matrix elements of O* and are termed Partition Coefficients. Since the structure of the excluded symmetry classes is independent of the quantization of O*, these Partition Coefficients can be used to define the values of the matrix elements of O* without reference to the form of its basis set. Thus, the choice of physical interpretation of the ligand field is unimportant. The strong field, weak field, Russell-Saunders and j-j coupling models are all unified in terms of the Partition Coefficients and the 3 symbols which are appropriate to the quantization.     

Thermal analysis of 5-halo-2'-deoxynucleosides

Heat may be a mutagenic agent which could be more important to evolution than are the ordinary errors in DNA replication. Therefore, it is necessary to know the stability of heredity determinants to thermal energy. Consequently, a thermal analysis, via differential scanning calorimetry (DSC), has been undertaken, using model compounds (crystalline 2'-deoxyribonucleosides and their 5-halo derivatives) to provide information regarding: 1. bond free energies maintaining the fibrous structure in nucleic acids e.g. H-bonding,π-complexing and dipole induced dipole interaction. 2. susceptibility to thermal degradation e.g. thermolytic cleavage of the glycosidic bond and deamination of the bases. Interpretation of the thermal curves has been facilitated and enhanced by utilization of a DSC-TLC analytical technique. Based on these data, a mechanism for the thermolysis of the glycosidic bond in the melt has been considered.     

Autoxidation of salvinorin A under basic conditions

[reaction: see text] Treatment of salvinorin A (1a) with KOH in MeOH gave the enedione 3, for which the dienone structure 7 was recently proposed. Also isolated, after methylation, were the secotriesters 4a-c. A mechanism for this unusual series of autoxidations is proposed. Surprisingly, 4a showed weak affinity at the kappa-opioid receptor. Divinatorins A-C (2a-c) showed no affinity at opioid receptors. Attempted reduction of 3 to a novel salvinorin diol (9d) was unsuccessful, but careful deacetylation of salvinorin C (9a) provided a viable route to this compound. A general method for identifying salvinorin 8-epimers by TLC is also presented.     

Exploring phase-transfer catalysis with molecular dynamics and 3D/4D quantitative structure-selectivity relationships

Quantitative Structure-Selectivity Relationships (QSSR) are developed for a library of 40 phase-transfer asymmetric catalysts, based around quaternary ammonium salts, using Comparative Molecular Field Analysis (CoMFA) and closely related variants. Due to the flexibility of these catalysts, we use molecular dynamics (MD) with an implicit Generalized Born solvent model to explore their conformational space. Comparison with crystal data indicates that relevant conformations are obtained and that, furthermore, the correct biphenyl twist conformation is predicted, as illustrated by the superiority of the resulting model (leave-one-out q(2) = 0.78) compared to a random choice of low-energy conformations for each catalyst (average q(2) = 0.22). We extend this model by incorporating the MD trajectory directly into a 4D QSSR and by Boltzmann-weighting the contribution of selected minimized conformations, which we refer to as '3.5D' QSSR. The latter method improves on the predictive ability of the 3D QSSR (leave-one-out q(2) = 0.83), as confirmed by repeated training/test splits.     

Covalent display of oligosaccharide arrays in microtiter plates

A covalent array for the display of complex oligosaccharides in microtiter plates has been developed. This strategy is conducive to the display of carbohydrates to proteins of interest such as lectins and antibodies, including the broadly neutralizing antibody 2G12 against HIV envelope oligomannose and can be cleaved from the surface for further characterization by mass spectrometry. The system was used to probe the multivalent interaction of 2G12 with an optimal epitope (Kd 0.1 muM).     

Crystal Structure and Thermogravimetric Analysis of Hexaaquazinc Triflate

The crystal structure of hexaaquazinc triflate is reported. The zinc center is surrounded by an octahedral environment of aqua ligands. The triflate anions occupy the second coordination sphere forming O–HO hydrogen bonds with the aqua ligands. Thermogravimetric analysis is consistent with six water molecules binding to the cation.