Synthesis and chiroptical properties of optically active photochromic methacrylic polymers bearing in the side chain the (S)-3-hydroxypyrrolidinyl group conjugated with the trans-azoaromatic chromophore

Novel optically active polymethacrylates, namely poly[(S)-3-methacryloyloxy-1-(4-azobenzene)pyrrolidine] and poly[(S)-3-methacryloyloxy-1-(4′-nitro-4-azobenzene)pyrrolidine], have been synthesized by radical polymerization of the corresponding monomers, prepared in turn through a synthetic route preserving the asymmetric center by any racemization reaction. These homopolymers are characterized by the presence in the side chain of an optically active pyrrolidinyl ring linked to the trans-azoaromatic system through the nitrogen atom. The optical activity of the polymers in solution appears much higher than that observed with the low molecular weight models, purposely synthesized for comparison. Circular dichroism spectra of the synthesized products demonstrated that, in solution, the macromolecules assume highly homogeneous conformations with a prevailing chirality to a larger extent with respect to analogous systems previously investigated. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3257–3268, 1999     

A study on the interactions between coenzyme Q 0 and superoxide anion. Could ubiquinones mimic superoxide dismutase (SOD)?

An electrochemical study was carried out on 1,4-benzoquinone, duroquinone, coenzymes Q ₀ and Q ₁₀ in the absence and in the presence of molecular oxygen in aprotic (DMF) and protic (DMF/H₂O 95:5 (v/v)) media. Water was added because the investigated reactions are deeply influenced by the presence of protons. Q ₀ and Q ₁₀ exhibited a similar electrochemical behaviour. Since Q ₀ is more soluble in protic medium than the biologically more important analogue Q ₁₀ , it was chosen as a model for a more detailed investigation. Voltammetric studies of Q ₀ carried out in aprotic and protic media in the presence of oxygen showed that, besides simple O₂ ^·− dismutation, the Q ₀ promoted dismutation of O₂ ^·− should also be considered. Spectroelectrochemical experiments with the same experimental conditions support the electrochemical results, showing that in the presence of superoxide and in aprotic medium semiquinone Q ₀ ^·− gives rise to a disproportionation equilibrium, while in the presence of water it tends to be reoxidized to the starting Q ₀ by OOH^·. EPR measurements are also in agreement with these results.     

Metal-sensitive and thermostable trypsin from the crevalle jack (<Emphasis Type="Italic">Caranx hippos</Emphasis>) pyloric caeca: purification and characterization

Background

Over the past decades, the economic development and world population growth has led to increased for food demand. Increasing the fish production is considered one of the alternatives to meet the increased food demand, but the processing of fish leads to by-products such as skin, bones and viscera, a source of environmental contamination. Fish viscera have been reported as an important source of digestive proteases with interesting characteristics for biotechnological processes. Thus, the aim of this study was to purify and to characterize a trypsin from the processing by-products of crevalle jack (Caranx hippos) fish.

Results

A 27.5 kDa trypsin with N-terminal amino acid sequence IVGGFECTPHVFAYQ was easily purified from the pyloric caeca of the crevalle jack. Its physicochemical and kinetic properties were evaluated using N-α-benzoyl-_DL-arginine-p-nitroanilide (BApNA) as substrate. In addition, the effects of various metal ions and specific protease inhibitors on trypsin activity were determined. Optimum pH and temperature were 8.0 and 50°C, respectively. After incubation at 50°C for 30 min the enzyme lost only 20% of its activity. K _m , k_cat, and k _cat /K _m values using BApNA as substrate were 0.689 mM, 6.9 s^-1, and 10 s^-1 mM^-1, respectively. High inhibition of trypsin activity was observed after incubation with Cd²⁺, Al³⁺, Zn²⁺, Cu²⁺, Pb²⁺, and Hg²⁺ at 1 mM, revealing high sensitivity of the enzyme to metal ions.

Conclusions

Extraction of a thermostable trypsin from by-products of the fishery industry confirms the potential of these materials as an alternative source of these biomolecules. Furthermore, the results suggest that this trypsin-like enzyme presents interesting biotechnological properties for industrial applications.

     

Microimaging FT-IR spectroscopy on pathological breast tissues

Microimaging Fourier transform infrared spectroscopy is able to monitor differentiation between normal and malignant tissues. All the specimens, previously submitted to histological analysis, displayed abnormal spectra compared with the corresponding normal tissues with changes in many diagnostic bands like those arising from phosphate, C–O and CH stretching vibrational modes. The comparison between cancer (K) and connective (C) spectra evidenced the following differences: in the vCH region 3000–2800 cm⁻¹ no hypomethylation effect was evident in K; the convolution of the bands of connective indicated an expected higher membrane fluidity; in the neoplastic zone, Amide I and II modes showed convoluted bands with maxima at 1651 and 1547 cm⁻¹, respectively, indicating an α-helix conformation of proteins due to changes in the secondary structure proteins upon carcinogenesis. Other signature bands, such as the deformation O–P–O phosphate band at 965 cm⁻¹, suggested DNA conformational changes in solid cancer, infiltrating cancer and neoplasia in the region 1350–800 cm⁻¹. These characteristic bands have been monitored as a function of the degree of cancer progression. Chemometric methods, such as principal component analysis (PCA) and hierarchical clustering analysis (HCA) have been used in order to distinguish spectra of neoplastic and normal zones.     

The Cahn–Hilliard–Hele–Shaw system with singular potential

The Cahn–Hilliard–Hele–Shaw system is a fundamental diffuse-interface model for an incompressible binary fluid confined in a Hele–Shaw cell. It consists of a convective Cahn–Hilliard equation in which the velocity u is subject to a Korteweg force through Darcy's equation. In this paper, we aim to investigate the system with a physically relevant potential (i.e., of logarithmic type). This choice ensures that the (relative) concentration difference φ takes values within the admissible range. To the best of our knowledge, essentially all the available contributions in the literature are concerned with a regular approximation of the singular potential. Here we first prove the existence of a global weak solution with finite energy that satisfies an energy dissipative property. Then, in dimension two, we further obtain the uniqueness and regularity of global weak solutions. In particular, we show that any two-dimensional weak solution satisfies the so-called strict separation property, namely, if φ is not a pure state at some initial time, then it stays instantaneously away from the pure states. When the spatial dimension is three, we prove the existence of a unique global strong solution, provided that the initial datum is regular enough and sufficiently close to any local minimizer of the free energy. This also yields the local Lyapunov stability of the local minimizer itself. Finally, we prove that under suitable assumptions any global solution converges to a single equilibrium as time goes to infinity.     

Non-linear response to an external AC drive near the Kosterlitz Thouless phase transition

We discuss the effect of an external AC drive on the motion of vortices near the vortex unbinding transition in two-dimensional superfluids, and on the motion of the interface between a crystal and its melt at the roughening transition. Both belong to the Kosterlitz Thouless class of phase transitions. There are three length scales in the problem: the correlation length, a diffusion length which varies as and a length inversely related to the strength of the drive. A possible resonance experiment for helium crystals is discussed.     

Photomodulation of the chiroptical properties of new chiral methacrylic polymers with side chain azobenzene moieties

We have investigated the photoinduced optical properties of a new class of chiral methacrylic polymers characterised by the presence in the side chain of an optically active pyrrolidinyl ring linked to a trans-azoaromatic system. The homopolymers are enantiomerically pure and their strong optical activity indicates that the macromolecules assume, both in solution and in solid thin films, highly homogeneous conformations with a prevailing chirality. As expected, the studied polymers exhibit reversible linear dichroism and birefringence when irradiated with linearly polarised light. By irradiating with circularly polarised light, we have discovered that it is possible to photomodulate the chiroptical properties of the polymer films. After irradiation with L-polarised light, the CD spectra of the films show a net inversion of their relative sign. The effect is reversible and the original shape of the CD spectra can be restored by pumping with R-polarised radiation. This unexpected new phenomenon can be explained in terms of the ability of the L-polarised radiation to invert the prevailing helicity of the polymeric chains. The observed effect seems to open new possibilities for the use of azobenzene-containing materials as chiroptical switches.     

Recycling of carbon fiber reinforced composite waste to close their life cycle in a cradle-to-cradle approach

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Molecular complexes of hydrazides with copper(II)

Summary The reaction of substituted hydrazides with copper(II) chloride was investigated in the solid state or in solution in order to account for substituent effects. Spectroscopic results and values of the formation constants indicate the occurrence of strong complexes.

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Molekulare Komplexe von Hydraziden mit Kupfer(II)

Zusammenfassung Die Reaktionen von substituierten Hydraziden mit Kupfer(II)chlorid wurden im Festzustand und in Lösung untersucht. Die spektroskopischen Ergebnisse und die Werte der Bildungskonstanten zeigen die Koordinierung zu starken Komplexen an.