Comparison of HPLC enantioseparation of substituted binaphthyls on CD‐, polysaccharide‐ and synthetic polymer‐based chiral stationary phases

Retention and enantioseparation behavior of ten 2,2′‐disubstituted or 2,3,2′‐trisubstituted 1,1′‐binaphthyls and 8,3′‐disubstituted 1,2′‐binaphthyls, which are used as catalysts in asymmetric synthesis, was investigated on eight chiral stationary phases (CSPs) based on β‐CD, polysaccharides (tris(3,5‐dimethylphenylcarbamate) cellulose or amylose CSPs) and new synthetic polymers (trans‐1,2‐diamino‐cyclohexane, trans‐1,2‐diphenylethylenediamine and trans‐9,10‐dihydro‐9,10‐ethanoanthracene‐(11S,12S)‐11,12‐dicarboxylic acid CSPs). Normal‐, reversed‐phase and polar‐organic separation modes were employed. The effect of the mobile phase composition was examined. The enantiomeric separation of binaphthyl derivatives, which possess quite similar structures, was possible in different enantioselective environments. The substituents and their positions on the binaphthyl skeleton affect their properties and, as a consequence, the separation system suitable for their enantioseparation. In general, the presence of ionizable groups on the binaphthyl skeleton, substitution with non‐identical groups and a chiral axis in the 1,2′ position had the greatest impact on the enantiomeric discrimination. The 8,3′‐disubstituted 1,2′‐binaphthyl derivatives were the most easily separated compounds in several separation systems. From all the chiral stationary phases tested, cellulose‐based columns were shown to be the most convenient for enantioseparation of the studied analytes. However, the polymeric CSPs with their complementary behavior provided good enantioselective environments for some derivatives that could be hardly separated in any other chromatographic system.     

Use of a polar ionic liquid as second column for the comprehensive two-dimensional GC separation of PCBs

The orthogonality of three columns coupled in two series was studied for the congener specific comprehensive two-dimensional GC separation of polychlorinated biphenyls (PCBs). A non-polar capillary column coated with poly(5%-phenyl–95%-methyl)siloxane was used as the first (¹D) column in both series. A polar capillary column coated with 70% cyanopropyl-polysilphenylene-siloxane or a capillary column coated with the ionic liquid 1,12-di(tripropylphosphonium)dodecane bis(trifluoromethane-sulfonyl)imide were used as the second (²D) columns. Nine multi-congener standard PCB solutions containing subsets of all native 209 PCBs, a mixture of 209 PCBs as well as Aroclor 1242 and 1260 formulations were used to study the orthogonality of both column series. Retention times of the corresponding PCB congeners on ¹D and ²D columns were used to construct retention time dependences (apex plots) for assessing orthogonality of both columns coupled in series. For a visual assessment of the peak density of PCBs congeners on a retention plane, 2D images were compared. The degree of orthogonality of both column series was, along the visual assessment of distribution of PCBs on the retention plane, evaluated also by Pearson's correlation coefficient, which was found by correlation of retention times t_R,i,2D and t_R,i,1D of corresponding PCB congeners on both column series. It was demonstrated that the apolar + ionic liquid column series is almost orthogonal both for the 2D separation of PCBs present in Aroclor 1242 and 1260 formulations as well as for the separation of all of 209 PCBs. All toxic, dioxin-like PCBs, with the exception of PCB 118 that overlaps with PCB 106, were resolved by the apolar/ionic liquid series while on the apolar/polar column series three toxic PCBs overlapped (105 + 127, 81 + 148 and 118 + 106).     

Invariance of the dissipative action at ultrahigh strain rates above the strong shock threshold

We have directly resolved shock structures in pure aluminum in the first few hundred picoseconds subsequent to a dynamic load at peak stresses up to 43 GPa and strain rates in excess of 10(10) s(-1). For strong shocks we obtain peak stresses, strain rates, and rise times. From these data, we directly validate the invariance of the dissipative action in the strong shock regime, and by comparing with data obtained at much lower strain rates show that this invariance is observed over at least 5 orders of magnitude in the strain rate. Over the same range, we similarly validate the fourth-power scaling of the strain rate with the peak stress (the Swegle-Grady relation).     

Measurement of the neutrino mass splitting and flavor mixing by MINOS

Measurements of neutrino oscillations using the disappearance of muon neutrinos from the Fermilab NuMI neutrino beam as observed by the two MINOS detectors are reported. New analysis methods have been applied to an enlarged data sample from an exposure of 7.25×10(20) protons on target. A fit to neutrino oscillations yields values of |Δm(2)|=(2.32(-0.08)(+0.12))×10(-3) eV(2) for the atmospheric mass splitting and sin(2)(2θ)>0.90 (90% C.L.) for the mixing angle. Pure neutrino decay and quantum decoherence hypotheses are excluded at 7 and 9 standard deviations, respectively.     

Total CO<Subscript>2</Subscript> measurements in horses: where to draw the line

Racehorses given a slurry of sodium bicarbonate (known colloquially as a ‘milkshake’) before a race have elevated concentrations of carbon dioxide in their blood. Racing administrators have reacted to this attempt to enhance the performance of the animal by setting limits to ‘total carbon dioxide’ (TCO2, the sum of carbon dioxide, carbonic acid, carbonate and bicarbonate) in prerace samples of plasma. The threshold limit for TCO2 in the rules of racing is an amount concentration of 36.0 mmol/L, with further action ensuing if the reported concentration is greater than an action limit that is calculated from the knowledge of the measurement uncertainty. At present in Australia, the action limit is 37.0 mmol/L, which is based on a combined standard measurement uncertainty of 0.22 mmol/L. From data obtained in a 1997 study in 515 normal racehorses, we have established the distribution (as a probability density function, PDF) of TCO2. This is combined with data from Australian laboratories of 126 horses that were tested following a positive screen, out of which 78 were confirmed positive. We employ the maximum entropy method to establish the PDFs and then apply Bayes Theorem to answer the question ‘given the measured TCO2 concentration what is the probability that a horse has been administered bicarbonate’? The distributions are not normal, which precludes simple approaches that calculate standard deviations from the data. For an action level of 37.0 mmol/L, there is a chance of only 1 in 2 020 000 that a nondoped horse will be judged to be doped, which implies this present threshold is unlikely to lead to conviction of an innocent trainer.     

Valuation formulae for window barrier options

In this paper we study window barrier options, where a single constant continuously-monitored barrier prevails for a period that commences strictly after the start date of the option and terminates strictly before expiry. We determine valuation formulae within a limited deterministic term-structure in terms of trivariate normal distribution functions. These formulae offer a generalization of the valuation formulae for partial barrier options given by Heynan and Kat.     

Unimodal betti numbers for a class of nilpotent lie algebras

In this paper we prove that all finite dimens~onal complex nilpotent Lie algebras containing an abelian ideal of codimension 1 have unirnodal Betti numbers.     

Weakly Bound States of Polar Molecules in Bilayers

We investigate a system of two polarized molecules in a layered trap. The molecules reside in adjacent layers and interact purely via the dipole?Cdipole interaction. We determine the properties of the ground state of the system as a function of the dipole moment and polarization angle. A bound state is always present in the system and in the weak binding limit the bound state extends to a very large distance and shows universal behavior.