Electronic spectral and photophysical properties of some p-phenylenevinylene oligomers in solution and thin films

A comprehensive photophysical and spectroscopic study of a new class of p-phenylenevinylene oligomers (PPV-trimers) possessing different alkyl and alkyloxy sidechain substituents and different end groups (aldehyde, CC, phenylene and anthracene units) was undertaken in solution at room temperature (293 K), low temperature (77 K) and in thin films. The study comprises absorption, emission and triplet–triplet absorption spectra, together with quantitative measurements of quantum yields (fluorescence, intersystem crossing, internal conversion and singlet oxygen formation) and lifetimes. The data allow the determination of rate constants for all decay processes. From these, several conclusions could be drawn. Changing from alkyl to alkyloxy substituents does not change fluorescence and internal conversion yields but decreases the (already small) intersystem crossing yield. The introduction of anthracene at the terminal ends of the PPV-trimers leads to the lowest fluorescence yield reported in this study. Of particular importance is the fact that the fluorescence quantum yields in films are of the same order of magnitude as those in solution, which suggests the potential for use of these oligomers for light-emitting device applications. With one of the alkyloxy derivatives, a more detailed study of the early part of the fluorescence decay was made, and it was found that upon excitation a fast conformational relaxation process of the initially excited oligomer occurs, leading to a more planar conjugation segment.     

Analysis of Colubroidea snake venoms by liquid chromatography with mass spectrometry: evolutionary and toxinological implications

The evolution of the venomous function of snakes and the diversification of the toxins has been of tremendous research interest and considerable debate. It has become recently evident that the evolution of the toxins in the advanced snakes (Colubroidea) predated the evolution of the advanced, front-fanged delivery mechanisms. Historically, the venoms of snakes lacking front-fanged venom-delivery systems (conventionally grouped into the paraphyletic family Colubridae) have been largely neglected. In this study we used liquid chromatography with mass spectrometry (LC/MS) to analyze a large number of venoms from a wide array of species representing the major advanced snake clades Atractaspididae, Colubrinae, Elapidae, Homalopsinae, Natricinae, Psammophiinae, Pseudoxyrhophiinae, Xenodontinae, and Viperidae. We also present the first sequences of toxins from Azemiops feae as well as additional toxin sequences from the Colubrinae. The large body of data on molecular masses and retention times thus assembled demonstrates a hitherto unsuspected diversity of toxins in all lineages, having implications ranging from clinical management of envenomings to venom evolution to the use of isolated toxins as leads for drug design and development. Although definitive assignment of a toxin to a protein family can only be done through demonstrated structural studies such as N-terminal sequencing, the molecular mass data complemented by LC retention information, presented here, do permit formulation of reasonable hypotheses concerning snake venom evolution and potential clinical effects to a degree not possible till now, and some hypotheses of this kind are proposed here. The data will also be useful in biodiscovery.     

VISIBLE CHEMILUMINESCENCE ASSOCIATED WITH THE REACTION BETWEEN METHEMOGLOBIN OR OXYHEMOGLOBIN WITH HYDROGEN PEROXIDE

Abstract Visible chemiluminescence is emitted in the irreversible deactivation of hemoglobin or methemoglobin with excess H₂O₂. The emission takes place in two phases. The most intense one lasts a few seconds and is followed by a second phase of lower intensity that remains for longer periods. This second phase presents chaotic or sustained oscillations. Free radicals are implicated in the luminescent process since the emission can be reduced by free radical scavengers such as 6-hydroxy-2,5,7,8,-tetramethylchroman-2-carboxylic acid (Trolox) or ascorbic acid. These additives lead to a delay in reaching the maximum intensity, which can be related to their consumption, implying substantial recycling of the hemoprotein. Chemiluminescence is also observed in the oxidation of hemin by H₂O₂, suggesting a role for the heme group in the processes leading to the excited state production. The lower intensity observed in the presence of hemin can be related to the contribution of the globin chains.     

PHEMA hydrogels obtained by a novel low-heat curing procedure with a potential for in situ preparation

In this work, we report on poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels obtained by a low heat curing reaction. These materials are suitable for in situ preparation and therefore endowed with a potential for several biomedical applications. The novel procedure adopted involves as the first step the synthesis of a soluble oligomeric PHEMA precursor containing polymerizable functions as side substituents. As the second step, the precursor is dissolved in equal amounts of 2-hydroxyethyl methacrylate (HEMA) and water, to form a viscous but still injectable syrup. A low temperature water soluble initiator is then added. The curing reaction starts promptly and is completed within few minutes. During the entire process the internal temperature never rises above 40 degrees C. Preliminary mechanical characterizations performed on the hydrogels in their water-swollen state and diffusion tests in absorption/desorption experiments clearly indicated that on all respects the novel hydrogels are comparable with conventional PHEMA hydrogels obtained according to literature from HEMA in the presence of divinyl crosslinkers. However, the much shorter curing time combined with the far lower curing temperature endow the new hydrogels with a higher potential in view of specific surgical requirements, and particularly for in situ preparation.     

Phase diagram of softly repulsive systems: the Gaussian and inverse-power-law potentials

We redraw, using state-of-the-art methods for free-energy calculations, the phase diagrams of two reference models for the liquid state: the Gaussian and inverse-power-law repulsive potentials. Notwithstanding the different behaviors of the two potentials for vanishing interparticle distances, their thermodynamic properties are similar in a range of densities and temperatures, being ruled by the competition between the body-centered-cubic (bcc) and face-centered-cubic (fcc) crystalline structures and the fluid phase. We confirm the existence of a reentrant bcc phase in the phase diagram of the Gaussian-core model, just above the triple point. We also trace the bcc-fcc coexistence line of the inverse-power-law model as a function of the power exponent n and relate the common features in the phase diagrams of such systems to the softness degree of the interaction.     

FTIR and WAXS analysis of periodate oxycellulose: Evidence for a cluster mechanism of oxidation

Cellulose paper (Whatman no.1, chromatographic grade) was oxidised with 0.1 M sodium metaperiodate at different oxidation levels (0–11 days at room temperature), and analysed with FTIR before and after chemical treatments (reduction, further oxidation, alkaline hydrolysis). The deconvolution of infrared data allowed us to verify that periodate oxidises cellulose in isolated domains, leading to the decrease of crystallinity, in agreement with the results of wide angle X-ray scattering (WAXS). In particular, the alkaline hydrolysis (β-alkoxy fragmentation) followed by mild acid treatment removed the oxidised groups and recovered most of the crystallinity of cellulose, as determined by the FTIR crystallinity index.     

Analysis of saccharides in beer samples by flow injection with electrospray mass spectrometry

Saccharides in foods play important roles, as they are essential substrates for fermentation processes. In brewing, the concentration of maltooligosaccharides influences the characteristics of beers and therefore their determination is of great practical interest. Electrospray ionization mass spectrometry (ESI-MS) was applied to identify and characterise maltooligosaccharides in beer samples. The effects due to different cation concentrations and dilution of samples were studied. Furthermore, quantitative analyses of maltooligosaccharides by means of flow-injection ESI-MS (FI/ESI-MS) of 1-microL beer samples (diluted 1000-fold) are described.     

5-vinylisoxazole

Cycloaddition of fulminic acid to 1-butyn-3-ol gave a mixture of 5-α-hydroxyethylisoxazole (I) and 4-α-hydroxyethylisoxazole (II) in the ratio 9:1. By the dehydration of 1, 5-vinylisoxazole (III) was obtained. Compound III has also been prepared by cyclization of 4-penten-2-ynal as well as its diethylacetal with hydroxylamine hydrochloride; in both instances no isomers have been obtained. Compound III spontaneously polymerizes even at room temperature yielding a polymer still containing isoxazole rings.     

Acid-base equilibria in organic solvents : Part 2. Cyclic voltammetry in the study of hydrogen-bond formation

The cyclic voltammetric technique is used to study hydrogen-bond formation in some polar organic solvents (S) of electroanalytical interest (1,2-dimethoxy, tetrahydrofuran, dimethylformamide, dimethyl sulphoxide and pyridine). The cathodic shift of the proton reduction caused by stepwise addition of the solvent investigated to a solution of anhydrous perchloric acid in acetonitrile is utilized. The theoretical treatment applied produced evidence that HS⁺ and HS⁺₂ are the only acidic species involved, so that the relevant formation constants can be evaluated. The data obtained mostly compare well with those available in the literature. The features that condition the tendency to hydrogen-bonding and the effect of hydrogen bonding on solvent basicity are discussed.