Small molecule probes finely differentiate between various ds- and ss-DNA and RNA by fluorescence,CD and NMR response

Two small molecules showed intriguing properties of analytical multipurpose probes, whereby one chromophore gives different signal for many different DNA/RNA by application of several highly sensitive spectroscopic methods. Dyes revealed pronounced fluorescence ratiomeric differentiation between ds-AU-RNA, AT-DNA and GC-DNA in approximate order 10:8:1. Particularly interesting, dyes showed specific fluorimetric response for poly rA even at 10-fold excess of any other ss-RNA, and moreover such emission selectivity is preserved in multicomponent ss-RNA mixtures. The dyes also showed specific chiral recognition of poly rU in respect to the other ss-RNA by induced CD (ICD) pattern in visible range (400–500 nm), which was attributed to the dye-side-chain contribution to binding (confirmed by absence of any ICD band for reference compound lacking side-chain). Most intriguingly, minor difference in the side-chain attached to dye chromophore resulted in opposite sign of dye-ICD pattern, whereby differences in NMR NOESY contacts and proton chemical shifts between two dye/oligo rU complexes combined with MD simulations and CD calculations attributed observed bisignate ICD to the dimeric dye aggregate within oligo rU.     

A note on convex dependence of solutions of IVPs relative to initial values

We generalize a result of Lakshmikantham, Shahzad and Walter on convex dependence of the solutions of IVPs with respect to the initial value to general ordered Banach spaces.     

Input-output systems in biology and chemistry and a class of mathematical models describing them

Our aim is to show a class of mathematical models in application to some problems of cell biology. Typically, our models are described via classical chemical networks. This property is visualized by a conservation law. Mathematically, this conservation law guarantees most of the mathematical properties of the models such as global existence and uniqueness of solutions as well as positivity of the solutions for positive data. These properties are consequences of the fact that the infinitesimal generators forming the underlying dynamical systems are (nonlinear) negative M-operators.This work was partially supported by the Grant Agency of the Czech Republic under contract No. 201/05/0453, the Information Society project No. 1ET400300415, and the grant of the Ministry of Education, Youth and Sports of the Czech Republic No. MSM 6840770010.     

Inherent peak compression of charged analytes in electrochromatography

This work resolves peak compression of charged analytes in CEC with strong cation‐exchange stationary phase particles. By combining electrochromatographic peak shape analysis with the results of numerical simulations and confocal laser scanning microscopy in the packed capillaries, we identify electrical field‐induced concentration polarization as the key physical phenomenon responsible for the inherent existence of local electrical field gradients on the scale of an individual support particle. Consequently, positive and negative field gradients exist between and inside the particles along the whole packing. Their intensity depends on the particles cation‐selectivity (governed by the particles volume charge density and the mobile phase ionic strength) and the applied field strength. The interplay of these local field gradients with the analytes retention (intraparticle adsorption) determines whether fronting, tailing, or spiked analyte peaks are observed, and it provides a mechanism by which strongly retained analytes can be eluted over long distances with little zone dispersion. Our analysis explains the “anomalous” peak compression effects with strong cation‐exchange particles, which have been reported more than a decade ago (Smith, N. W., Evans, M. B., Chromatographia 1995, 41, 197–203) and since then remained largely unresolved.