Orthogonality and similarity within silica-based reversed-phased chromatographic systems

The starting point of this study was a current set of 32 chromatographic systems used to select initial conditions for method development to determine the impurity profile of a drug. The system exhibiting the best selectivity is then selected for further method development. In this current set eight silica-based phases are applied in conjunction with four mobile phases at different pH. In order to save time and resources, the possibilities for a meaningful subset selection were investigated. The most differing systems in terms of selectivity, in other words only the most orthogonal systems, need to be selected. Since the stationary phases are all silica-based, the selectivity differences are examined within a more homogeneous group than if, for instance, also zirconia- or polymer-based columns would be involved. To select the subset of systems also the best overall separation performances are taken into account. The selection is based both on the HPLC-DAD data of a generic set of 68 drugs, and on the LC-MS-DAD results for a mixture of 15 drugs, less different in structure. The orthogonality is evaluated using weighted-average-linkage dendrograms and color maps, both created from the Pearson-correlation coefficients r between normalized retention times r. The Derringer's desirability functions are applied to define the systems with the best overall separation performances. Proposals for different representative subsets of the initial 32 systems are made.     

Density fluctuations in the presence of spinodal instabilities

Density fluctuations resulting from spinodal decomposition in a nonequilibrium first-order chiral phase transition are explored. We show that such instabilities generate divergent fluctuations of conserved charges along the isothermal spinodal lines appearing in the coexistence region. Thus, divergent density fluctuations could be a signal not only for the critical end point but also for the first-order phase transition expected in strongly interacting matter. We also compute the mean-field critical exponent at the spinodal lines. Our analysis is performed in the mean-field approximation to the Nambu-Jona-Lasinio model formulated at finite temperature and density. However, our main conclusions are expected to be generic and model independent.     

The functional renormalization group and O(4) scaling

The critical behavior of the chiral quark-meson model is studied within the Functional Renormalization Group (FRG). We derive the flow equation for the scale-dependent thermodynamic potential at finite temperature and density in the presence of a symmetry-breaking external field. We perform a set of approximations to formulate and solve the FRG flow equation in the presence of fermionic degrees of freedom and test their influence on the O(4) critical properties expected in the quark-meson model. Within this scheme, the critical scaling behavior of the order parameter, its transverse and longitudinal susceptibilities as well as the correlation lengths near the chiral phase transition are computed for vanishing baryon density. We focus on the scaling properties of these observables at non-vanishing external field when approaching the critical point from the symmetric as well as from the broken phase. We confront our numerical results with the Widom–Griffiths form of the magnetic equation of state, obtained by a systematic ε expansion of the scaling function.     

Picosecond thermometer in the amide I band of myoglobin

The amide I and II bands in myoglobin show a heterogeneous temperature dependence, with bands at 6.17 and 6.43 microm which are more intense at low temperatures. The amide I band temperature dependence is on the long wavelength edge of the band, while the short wavelength side has almost no temperature dependence. We compare concepts of anharmonic solid-state crystal physics and chemical physics for the origins of these bands. We suggest that the long wavelength side is composed of those amino acids which hydrogen bond to the hydration shell of the protein, and that temperature dependent bands can be used to determine the time it takes vibrational energy to flow into the hydration shell. We determine that vibrational energy flow to the hydration shell from the amide I takes approximately 20 ps to occur.     

The onset of deconfinement inSU(2) lattice gauge theory

InSU(2) lattice gauge theory, we study deviations from ideal gas behaviour near the deconfinement point. On lattices of sizeN _σ ³ ×4,N _σ=8, 12, 18 and 26, we calculate the quantityΔ≡(ε?3P)/T ⁴. It increases sharply just aboveT _c , peaks atT/T _c =1.15 ±0.05 and then drops quickly. This form of behaviour is shown to be the consequence of a second order phase transition. Dynamically it could arise because just aboveT _c , the low momentum states of the system are remnant massive modes rather than deconfined massless gluons.