Determination of potential curve parameters of excited electronic states of polyatomic molecules by resonance CARS

Resonance CARS line-shape analysis has been applied to determine the parameters of the excited electronic state potential curves of a cyanine dye and its short-lived photoisomers during the process of photoisomerization. For this very complicated situation other methods for the estimation of these values would fail. The origin shift parameters determined are very small and the homogeneous line width is smaller than the line width of the absorption band.     

Liquid crystal polymers 23. Steric and polar effects of large substituents in thermotropic aromatic polyesters with decamethylene spacers

A series of thermotropic aromatic polyesters based on a triad ester mesogenic unit containing an arylsulfonyl substituted hydroquinone group and a decamethylene spacer group was prepared. The large arylsulfonyl substituent was substituted in the para-position with either electron donating or accepting groups to study the effect of steric and polar interactions on the thermal transitions of these polymers and on the thermodynamic parameters of their isotropization transitions. All polymers formed nematic melts, and a regular decrease in T₁, ΔH₁ and ΔS₁ was observed with increasing molecular radius of the substituted hydroquinone group. However, a polarity or polarizability effect was superimposed on these relationships. Model compounds containing the same aromatic ester triad were prepared and their thermotropic properties were compared to those of the polymers. Essentially identical effects were observed for both.     

Synthesis of stereoregular poly(alkyl malolactonates)

Optically pure methyl, ethyl, isopropyl, and benzyl (R)-malolactonate were prepared from (S)-(-)-malic acid and were polymerized in the bulk with tetraethylammonium benzoate as the initiator to yield high-molecular-weight, crystalline polymers. The optical purity of methyl and benzyl malolactonate was determined by ¹H NMR spectroscopy of the β-lactone complexed with a chiral europium shift reagent. Enantiomeric excesses of 100% were found (the experimental error was 3%). Optically active poly(β-malic acid) was obtained from optically active poly[benzyl (S)-malate] by catalytic hydrogenolysis of the pendent benzyl esters. Ethyl and benzyl (R)-malolactonate were also copolymerized, and the benzyl esters of the resulting copolymer were converted into carboxylic acid units by hydrogenolysis.     

High hydrostatic pressure inactivation of Lactobacillus plantarum cells in (O/W)-emulsions is independent from cell surface hydrophobicity and lipid phase parameters

Inactivation efficiency of high hydrostatic pressure (HHP) processing of food is strongly affected by food matrix composition. We investigated effects of fat on HHP inactivation of spoilage-associated Lactobacillus (L.) plantarum strains using defined oil-in-water (O/W)-emulsion model systems. Since fat-mediated effects on HHP inactivation could be dependent on interactions between lipid phase and microbial cells, three major factors possibly influencing such interactions were considered, that is, cell surface hydrophobicity, presence and type of surfactants, and oil droplet size. Pressure tolerance varied noticeably among L. plantarum strains and was independent of cell surface hydrophobicity. We showed that HHP inactivation of all strains tended to be more effective in presence of fat. The observation in both, surfactant-stabilized and surfactant-free (O/W)-emulsion, indicates that cell surface hydrophobicity is no intrinsic pressure resistance factor. In contrast to the presence of fat per se, surfactant type and oil droplet size did not affect inactivation efficiency.     

Fluctuation measurements in a supersonic boundary layer implying in-situ calibration of the hot-wire anemometer

A calibration technique for the constant-temperature hot-wire anemometer is presented, which is based on traversing the probe through the boundary layer of a flat plate while simultaneously performing fluctuation measurements. The free stream Mach number was M = 2.54, and the Reynolds number Re_d, based on wire diameter, ranged from 9 to 23. A comparison of the sensitivity values obtained with the aid of such a calibration procedure — under the condition of neglecting low temperature loadings (t<0.6) — agrees well with sensitivities determined with free-stream data-The use of a modified transfer function for correcting the power spectra of flow perturbations revealed a conformity of wide parts of the corrected spectra with the Kolmogorov decay. The fluctuation levels of total temperature and mass flux were computed for the boundary layer of a flat plate. This work was presented at the International Conference on the Methods of Aerophysical Research ICMAR 2007, which was held in Novosibirsk on 5–10 February 2007.     

Experimental investigation of Risken–Nummedal–Graham–Haken laser instability in fiber ring lasers

It has been suggested (by Pessina et al. in 1997) that the observed spontaneous mode beating of erbium-doped-fiber ring lasers can be explained as the multimode instability described in 1968 by Risken and Nummedal and by Graham and Haken (the RNGH instability), which is based on Rabi-splitting-induced gain. If true, this would constitute the first ever example of this instability in an actual experiment. We test the hypothesis through a quantitative experimental investigation. We demonstrate that there is indeed a clear, marked onset of the instability, a fact that went unnoticed in all previous experiments because it is very close to the lasing threshold. We intentionally raise cavity loss to better separate onset of lasing and of instability. We obtain quantitative information on the instability onset. An interpretation as the predicted second threshold is reasonable provided inhomogeneous gain line broadening is taken into account. We also observe that instability above its onset exists only intermittently; this may hint at a subcritical bifurcation and noise-driven transitions. In any event, the RNGH mechanism is present, if not in a pure form. PACS 42.65.Sf; 42.60.Mi; 42.55.Wd     

Detection of protein-RNA crosslinks by nanoLC-ESI-MS/MS using precursor ion scanning and multiple reaction monitoring (MRM) experiments

Protein-RNA interactions within ribonucleoprotein particles (RNPs) can be investigated by UV-induced crosslinking of proteins to their cognate RNAs and subsequent isolation and mass-spectrometric analysis of crosslinked peptide-RNA oligonucleotides. Because of the low crosslinking yield, a major challenge in protein-RNA UV crosslinking is the detection of the crosslinked species over the excess of non-crosslinked material, especially when complex systems (native RNPs) are investigated. Here, we applied a novel approach that uses on-line nanoLC-ESI-MS/MS to detect and subsequently sequence peptide-RNA oligonucleotide crosslinks from crude mixtures. To detect the crosslinks we made use of features shared by crosslinks and phosphopeptides, that is, the phosphate groups that both carry. A precursor ion scan for m/z 79 (negative-ion mode, -ve) is applied to selectively detect analytes bearing the phosphate-containing species (i.e., residual non-crosslinked RNA and peptide-RNA crosslinks) from crude mixtures and to determine their exact m/z values. On this basis, a multiple reaction monitoring (MRM) experiment monitors the expected decomposition from the different precursor charge states of the putative crosslinks to one of the four possible RNA nucleobases [m/z 112, 113, 136, 152 (positive-ion mode, +ve)]. On detection, a high-quality MS/MS is triggered to establish the structure of the crosslink. In a feasibility study, we detected and subsequently sequenced peptide-RNA crosslinks obtained by UV-irradiation of (1) native U1 snRNPs and (2) [15.5K-61K-U4atac] snRNPs prepared by reconstitution in vitro. MRM-triggered collision-induced dissociation (CID) MS/MS enabled us to obtain sequence information about the crosslinked peptide and RNA moiety.     

Liquid crystal polymers. 14. Synthesis and properties of thermotropic poly(1,4-alkylphenylene terephthalates)

A series of terephthalate polyesters was prepared from substituted hydroquinone monomers that contained a single cyclic or branched alkyl group. All the polymers were crystalline with melting points well below 400°C that decreased as the size of the cycloalkyl substituent increased. Most of the polymers had clearing temperatures below 400°C and all formed nematic melts. Copolyesters that contained equimolar amounts of two different substituted hydroquinone monomers, which were crystalline and had broad temperature ranges for nematic phase formation, were also prepared.