Dramatic selectivity differences in the association of DNA and RNA models with new ethylene- and propylene diamine derivatives and their copper complexes

The affinities of polyamines consisting of ethylenediamine units equipped with either one or two terminal naphthyl-, anthryl-, or acridyl units towards PolyA.PolyU as an RNA model, and Poly(dA).Poly(dT) as a DNA model are screened by measuring the melting point changes (DeltaT(m)) of the double strands, and also partially by a fluorimetric binding assay using ethidium bromide. The larger aromatic moieties with long spacers between them allow bisintercalation; this leads to an increased preference for DNA in comparison to RNA, where ion pairing of the ammonium centers with the major RNA groove phosphates dominates. Allosteric affinity control by metalation is achieved e.g. with Cu(2+) ions, which induce conformational distortions within the chains. With anthryl- in contrast to naphthyl derivatives intercalation can be so strong that distortion of the ethylenediamine chain by metalation is not powerful enough. A particularly high concentration of positive charges is accessible with tripodal derivatives built up from ethylenediamine and propylenediamine units; in the absence of aryl parts, which interfere with the RNA groove preference, one observes the highest affinity difference known until today, reflected in a melting point ratio of DeltaT(m(RNA))/DeltaT(m(DNA)) = 40, whereas other synthetic ligands reach only a DeltaT(m(RNA))/DeltaT(m(DNA)) ratio of about 3.     

VUV photon induced fluorescence study of SF5CF3

The interaction of SF(5)CF(3) with vacuum-UV radiation has been investigated by photon induced fluorescence spectroscopy. Total fluorescence yield and dispersed fluorescence spectra of SF(5)CF(3) were recorded in the 200-1000 nm fluorescence window. In all cases, the fluorescence spectra resemble those of CF(3)X (X = H, F, Cl, and Br) molecules. At photon energies below 20 eV, the emission is attributed to the excited CF(3) and CF(2) fragments. The threshold for the CF(3) emission is 10.2 +/- 0.2 eV, giving an upper limit estimate for the SF(5)-CF(3) bond dissociation energy of 3.9 +/- 0.3 eV. The excitation functions of the CF(3) and CF(2) emissions were measured in the photon energy range 13.6-27.0 eV. The resonant structures observed in SF(5)CF(3) are attributed to electronic transitions from valence to Rydberg orbitals, following similar assignments in CF(3)X molecules. The photoabsorption spectrum of SF(5)CF(3) shows features at the same energies, indicating a strong contribution from Rydberg excitations.     

ChemMatrix, a poly(ethylene glycol)-based support for the solid-phase synthesis of complex peptides

CM (ChemMatrix) resin is a new, totally poly(ethylene glycol) (PEG)-based resin, made exclusively from primary ether bonds and, therefore, highly chemically stable. It exhibits good loading and is user-friendly because of its free-flowing form upon drying. It performs excellently for the preparation of hydrophobic, highly structured, and poly-Arg peptides, as compared to polystyrene (PS) resins. In the most striking example, stepwise solid-phase assembly of the highly complex beta-amyloid (1-42) peptide resulted in a crude material of 91% purity. In contrast, literature procedures using PS or PEG-PS-based resins for this peptide required convergent approaches, additional time-consuming steps, or both. In addition to the difficulties of its synthesis, characterization of the beta-amyloid (1-42) peptide as a monomer is also a challenge, and methods for characterization by HPLC and MALDI-TOF have also been developed.     

Comparison of hydrogen bonding in 1-octanol and 2-octanol as probed by spectroscopic techniques

Liquid 1-octanol and 2-octanol have been investigated by infrared (IR), Raman, and Brillouin experiments in the 10-90 degrees C temperature range. Self-association properties of the neat liquids are described in terms of a three-state model in which OH oscillators differently implicated in the formation of H-bonds are considered. The results are in quantitative agreement with recent computational studies for 1-octanol. The H-bond probability is obtained by Raman data, and a stochastic model of H-bonded chains gives a consistent picture of the self-association characteristics. Average values of hydrogen bond enthalpy and entropy are evaluated. The H-bond formation enthalpy is ca. -22 kJ/mol and is slightly dependent on the structural isomerism. The different degree of self-association for the two octanols is attributed to entropic factors. The more shielded 2-isomer forms larger fractions of smaller, less cooperative, and more ordered clusters, likely corresponding to cyclic structures. Signatures of a different cluster organization are also evidenced by comparing the H-bond energy dispersion (HBED) of OH stretching IR bands. A limiting cooperative H-bond enthalpy value of 27 kJ/mol is found. It is also proposed that the different H-bonding capabilities may modulate the extent of interaggregate hydrocarbon interactions, which is important in explaining the differences in molar volume, compressibility, and vaporization enthalpy for the two isomers.     

Stereoselective synthesis of the cytotoxic macrolide FD-891

[reaction: see text] A total synthesis of the naturally occurring, cytotoxic macrolide FD-891 is described. Three fragments were first stereoselectively constructed using mainly asymmetric aldol and allylation reactions. The complete framework was then assembled using two Julia-Kocienski olefinations to connect the three fragments and a Yamaguchi reaction to close the macrolactone ring.     

Electrocatalytical properties of polymethylferrocenyl dendrimers and their applications in biosensing

The electrochemical characterization of polymethylferrocenyl dendrimers deposited onto a platinum electrode and their applications as hydrogen peroxide and glucose sensor are described. The redox dendrimers consist of flexible poly(propileneimine) dendrimer cores functionalised with octamethylferrocenyl units. Amperometric biosensors for glucose were prepared by immobilization of glucose oxidase onto these modified electrodes. The influence of the dendrimer generation and the thickness of the dendrimer layer, the effect of the substrate concentration, and the interferences and reproducibility on the response of the sensors were investigated.     

Further research on the photo-SPME of triclosan

In this study the photoinduced degradation of triclosan has been investigated by photo-solid-phase microextraction (photo-SPME). In photo-SPME, photodegradation is carried out on the SPME fibre containing the target compound. Triclosan was extracted from aqueous solutions by use of polydimethylsiloxane SPME fibres and these were subsequently exposed to UV irradiation (power 8 W, wavelength 254 nm) for different times (from 2 to 60 min). The photodegradation kinetics of triclosan were investigated, the photoproducts generated were tentatively identified, and the photochemical behaviour of these products was studied by use of this on-fibre approach followed by gas chromatographic–mass spectrometric analysis. Eight photoproducts were tentatively identified, including chlorinated phenols, chlorohydroxydiphenyl ethers, 2,8-dichlorodibenzo-p-dioxin, and a possible dichlorodibenzodioxin isomer or dichlorohydroxydibenzofuran. The main photodegradation mechanisms were postulated and photodegradation pathways proposed. The effect of pH on triclosan degradation and on triclosan-to-dioxin conversion was also investigated. Triclosan degradation occurred, and generation of 2,8-dichlorodibenzo-p-dioxin was confirmed, throughout the pH range studied (from 3 to 9).      

Near-infrared reflectance spectroscopy as a fast and non-destructive tool to predict foliar organic constituents of several woody species

Near-infrared reflectance spectroscopy (NIRS) was used to estimate N, neutral detergent fibre (NDF), acid detergent fibre (ADF), lignin and cellulose contents in leaves of a heterogeneous group of 17 woody species from the Central Western region of the Iberian Peninsula. The sample set consisted of 182 samples of leaves of deciduous and evergreen species, showing a wide range of concentrations determined by reference methods: 6.60–35.2 g kg⁻¹ (N), 15.5–66.0% (NDF), 10.2–57.3% (ADF), 3.45–27.4% (lignin) and 5.79–31.3% (cellulose). Reflectance spectra, obtained for samples of dried and ground leaves, were recorded as log1/R (R=reflectance) from 1,100 to 2,500 nm. NIRS calibrations were developed using multiple linear (MLR) and partial least-squares (PLSR) regressions, and tested by external validation. Spectral data were transformed to the first and second derivative (1D, 2D). The PLSR method and derivative transformations provided the best statistics and showed lower standard errors of calibration (SEC) and higher coefficients of multiple determination (R ²). In the external validation the standard errors of prediction (SEP) were 0.76 g kg⁻¹ (N), 2.11% (NDF), 1.47% (ADF), 0.85% (lignin) and 0.86% (cellulose). The results obtained show that NIRS is very effective for the estimation of these organic constituents in leaf tissue of woody species. This technique can be used in ecological or ecophysiological studies as an alternative to the more time-consuming standard methods.