The first member of the eleven-vertex azadicarbaborane series, 1,6,9-NC2B8H13, and its N-alkyl derivatives

Reactions between closo-1,2-C(2)B(8)H(10) (1) and amines of general formulation R(1)R(2)NH (where R(1), R(2) = H, H; Me, H; t-Bu, H and Et, Et) resulted in a straightforward cluster expansion and formation of the 11-vertex arachno-azadicarbaboranes of the 1,1-R(1),R(2-)1,6,9-NC(2)B(8)H(11) (2) cluster constitution (where R(1), R(2) = H, H 2a; Me, H 2b; t-Bu, H 2c and Et, Et 2d) in yields 10-75%, depending on the nature of the amine used. The reactions are the first example of a direct closo to arachno transformation in the area of cluster-boron compounds. Compounds 2b and 2c were isolated in two isomeric forms anti- and syn- that differ in the positioning of the t-Bu substituent with respect to the bridging hydrogen site. Deprotonation of compounds 2 generally leads to removal of the bridging proton and formation of the [1,1-R(1),R(2-)1,6,9-NC(2)B(8)H(11)](-) (2-) anions that, in the case of the monoalkylated Me and t-Bu derivatives, adopt only an anti configuration. The structure of anti-2c was determined by X-ray diffraction analysis and the geometries of the parent compound and the corresponding syn and anti isomers were optimised at the RMP2/6-31G* level. The composition of all compounds is consistent with the results of mass spectrometry and multinuclear ((1)H and (11)B) spectroscopy complemented by two-dimensional [(11)B-(11)B]-COSY and (1)H{(11)B(selective)} NMR measurements. Experimental (11)B chemical shifts generally show acceptable agreement with theoretical values calculated by GIAO methods, in particular at GIAO-MP2/II, where possible.     

Closure-based constraints in formal concept analysis

We present a method of imposing constraints in extracting formal concepts (equivalently, closed itemsets or fixpoints of Galois connections) from a binary relation. The constraints are represented by closure operators and their purpose is to mimic background knowledge a user may have of the data. The idea is to consider and extract only these itemsets that are compatible with the background knowledge. As a result, the method extracts less clusters, those that are interesting from the user point of view, in a shorter time. The method makes it also possible to extract minimal bases of attribute dependencies in the input data that are compatible with the background knowledge. We provide examples of several particular types of constraints including those that appeared in the literature in the past and present algorithms to compute the constrained formal concepts and attribute implications.     

Titania-based stationary phase in separation of ondansetron and its related compounds

Improvements in stationary phase stability have been and remain a great task for research of new stationary phases. Metal oxide-based stationary phases appear as one of perspective alternatives to classical silica based stationary phases regarding to their similar effectiveness, different selectivity, different retention mechanism and mainly better chemical and thermal stability. In this study, the retention behaviour of ondansetron and its five pharmacopoeial impurities on TiO(2)-based reversed phase was investigated. The influence of buffer type, pH and concentration on retention was studied. Different types and amount of organic solvent in mobile phase were tested. The effect of temperature and flow rate on separation was investigated. The separation conditions were optimized and developed method validated. The retention parameters - retention time (t(R)), retention factor (k'), theoretical plate number (N), resolution between peaks due to nearby peaks (R(s)) and symmetry factor (A(s)) have been compared to parameters achieved on polybutadiene-coated zirconia column. The thermodynamic parameters of retention of analysed compounds - enthalpy, entropy and Gibbs free energy - were calculated and compared to those achieved on polybutadiene-coated zirconia column. This work proves similarity of retention behaviour of ondansetron and its five related compounds on zirconia-based and titania-based stationary phases and potential utilisation of polyethylene covered TiO(2)-based reversed stationary phase as an alternative to polybutadiene-coated ZrO(2) stationary phase in pharmaceutical analysis of ondansetron.     

Dynamic Coating Agents in CE

In capillary electrophoresis (CE) dynamic coating agents are commonly used for manipulating or reversing electroosmotic flow (EOF) and suppressing adsorption of analytes by the silica surface. In this paper we review general aspects of dynamic coating in CE and discuss features and facts concerning formation of the EOF and determination of its magnitude.     

Aligned rank tests in measurement error model

Aligned rank tests are introduced in the linear regression model with possible measurement errors. Unknown nuisance parameters are estimated first and then classical rank tests are applied on the residuals. Two situations are discussed: testing about an intercept in the linear regression model considering the slope parameter as nuisance and testing of parallelism of several regression lines, i.e. whether the slope parameters of all lines are equal. Theoretical results are derived and the simulation study is also made to illustrate good performance of introduced tests.     

Strongly regular family of boundary-fitted tetrahedral meshes of bounded C2 domains

We give a constructive proof that for any bounded domain of the class C² there exists a strongly regular family of boundary-fitted tetrahedral meshes. We adopt a refinement technique introduced by K?í?ek and modify it so that a refined mesh is again boundary-fitted. An alternative regularity criterion based on similarity with the Sommerville tetrahedron is used and shown to be equivalent to other standard criteria. The sequence of regularities during the refinement process is estimated from below and shown to converge to a positive number by virtue of the convergence of q-Pochhammer symbol. The final result takes the form of an implication with an assumption that can be obviously fulfilled for any bounded C² domain.