Determination of the gas chromatographic elution sequences of the (+)- and (−)-enantiomers of stable atropisomeric PCBs on Chirasil-dex

Pure enantiomers of chiral (atropisomeric) polychlorinated biphenyls (PCBs) obtained by high-performance liquid chromatography were used to establish the gas chromatographic elution sequences of the (+)- and (−)-enantiomers of six PCB atropisomers on Chirasil-Dex. The elution order was found to be (−/+) for PCBs 84, 132, 136, and 176 and (+/−) for PCBs 135 and 174. The retention characteristics of all 19 tri- and tetra-ortho atropisomeric PCBs were also investigated. Nine of the atropisomers could be separated using this chiral selector. PCBs 95, 132, and 149 were completely resovled and PCBs 84, 91, 135, 136, 174, and 176 were partially separated (R = 0.7–0.9). All of the separated congeners are 2,3,6-substituted in at least one ring, and conversely – none of the congeners that lacks 2,3,6-substitution could be separated. Thus, chiral recognition and enantiomer separation seems to be strongly governed by 2,3,6-substitution.     

Chain transfer reactions in emulsion polymerization of butadiene/styrene

Calculation of regulating index r from M̄_W values determined by experiments is proposed. The calculation is based on the assumption that the M̄_W values only depend on the conversion and the regulating index in emulsion polymerization. On this basis the calculation of regulator concentration in the latex particles was also possible. M̄_W values calculated in this way and experimental M̄_W values show good agreement.     

Rank one transformations with singular spectral type

We show that a certain class of measures arising from generalized Riesz products is singular. In particular, cutting and stacking (i.e. rank one) transformations whose cuts do not grow too rapidly, have singular maximal spectral type. The precise condition is , wherew _h is the number of cuts at stagen. Supported by a Canada NSERC grant. Supported by an NSF grant.     

High-frequency 263 GHz PELDOR

Pulsed electron–electron double resonance (PELDOR/DEER) at high frequencies can provide information on the relative orientation of paramagnetic centres or spin labels, if those are rigidly oriented in a host biomolecule and experiments are performed with sufficient orientation selectivity. We present the first comparative PELDOR study at 263 and 94 GHz on a model RNA system containing rigid nitroxides. We show that at 263 GHz still considerable modulation depth is observed and orientation selectivity is significant, particularly in g _x–g _y plane of the nitroxides.     

A Chimeric DNA/RNA Antiparallel Quadruplex with Improved Stability

Nucleic acid quadruplexes are proposed to play a role in the regulation of gene expression, are often present in aptamers selected for specific binding functions and have potential applications in medicine and biotechnology. Therefore, understanding their structure and thermodynamic properties and designing highly stable quadruplexes is desirable for a variety of applications. Here, we evaluate DNA→RNA substitutions in the context of a monomolecular, antiparallel quadruplex, the thrombin-binding aptamer (TBA, GGTTGGTGTGGTTGG) in the presence of either K⁺ or Sr²⁺. TBA predominantly folds into a chair-type configuration containing two G-tetrads, with G residues in both syn and anti conformation. All chimeras with DNA→RNA substitutions (G→g) at G residues requiring the syn conformation demonstrated strong destabilization. In contrast, G→g substitutions at Gs with anti conformation increased stability without affecting the monomolecular chair-type topology. None of the DNA→RNA substitutions in loop positions affected the quadruplex topology; however, these substitutions varied widely in their stabilizing or destabilizing effects in an unpredictable manner. This analysis allowed us to design a chimeric DNA/RNA TBA construct that demonstrated substantially improved stability relative to the all-DNA construct. These results have implications for a variety of quadruplex-based applications including for the design of dynamic nanomachines.     

Carboxyl groups in pre-treated regenerated cellulose fibres

The influence of peroxide bleaching and slack-mercerization on the amount of acidic groups in regenerated fibres (viscose, modal and lyocell) were studied. Conductometric titration was used to determine the total content of acidic carboxylic groups. Polyelectrolyte titration was used for surface and total charge determination, and to obtain information about the charge distribution and accessibilities of charged groups. Changes in fibre crystallinity to pre-treatment processes were characterized using iodine sorption (Schwertassek method) and correlated to treatments and the amount of carboxylic groups. For all three types of fibres the amount of accessible carboxyl groups was lowered by an increase in the degree of crystallinity. Bleaching with hydrogen peroxide causes some oxidative cellulose damage and, therefore, a larger amount of carboxyl groups (presumably formed at the end of cellulose chains). Slack-mercerization did not significantly change the total amount of acidic groups in the fibres, but their accessibility to cationic polyelectrolytes, in particular to polymers with high molecular weight was substantially lowered. Lidija Fras Zemljič, Zdenka Peršin, and Karin Stana Kleinschek are the members of the European Polysaccharide Network of Excellence (EPNOE).     

Trans-cis isomerization is responsible for the red-shifted fluorescence in variants of the red fluorescent protein eqFP611

An important class of red fluorescent proteins (RFPs) feature a 2-iminomethyl-5-(4-hydroxybenzylidene)imidazolinone chromophore. Among these proteins, eqFP611 has the chromophore in a coplanar trans orientation, whereas the cis isomer is preferred by other RFPs such as DsRed and its variants. In the photoactivatable protein asFP595, the chromophore can even be switched from the nonfluorescent trans to the fluorescent cis state by light. By using X-ray crystallography, we have determined the structure of dimeric eqFP611 at high resolution (up to 1.1 A). In the far-red emitting eqFP611 variant d2RFP630, which carries an additional Asn143Ser mutation, the chromophore resides predominantly (approximately 80%) in the cis isomeric state, and in RFP639, which has Asn143Ser and Ser158Cys mutations, the chromophore is found completely in the cis form. The pronounced red shift of excitation and emission maxima of RFP639 can thus unambiguously be assigned to trans-cis isomerization of the chromophore. Among RFPs, eqFP611 is thus unique because its chromophore is highly fluorescent in both the cis and trans isomeric forms.