Novel cytotoxic brominated diterpenes from the red alga Laurencia obtusa

Five new brominated diterpenes, along with two known, have been isolated from the organic extract of the red alga Laurencia obtusa, collected from the coastal rocks of Preveza in the Ionean Sea, Greece. The novel metabolites prevezols B-E possess two new carbon skeletons, to the best of our knowledge, unprecedented in the literature. The structures and the relative stereochemistry of the new natural products were established by means of spectral data analyses. The new metabolites were tested for their cytotoxic activity against five human cell lines. Two metabolites have exhibited significant cytotoxicity.     

Ground-state energy of a two level system with phonon coupling

The coupling of a two-level system to quantized boson modes has been the focus of many researchers for a number of years. Applications to exciton motion, molecular polaron formation, chaos in quantum systems as well as a number of other effects in condensed matter physics have also been studied. Here we investigate the interaction of bosonic modes with a two-level fermionic system. This quantum system is used as a testing ground for a recently developed Generalized Moments Expansion, GMX(m,n), of which the well-known Connected Moments Expansion (CMX) and Alternate Moments Expansion (AMX) are special cases. The convergence and viability of this scheme are discussed and comparisons are made with a related Canonical Sequence Method (CSM) as well as a Lanczos tridiagonal truncation scheme.     

Twist-grain boundary phase induced by Au nanoparticles in a chiral liquid crystal host

We report on the stabilisation of the liquid-crystalline, twist-grain boundary A (TGB_A) phase in mixtures of a chiral liquid crystal and surface-functionalised spherical Au nanoparticles (NPs) of 10 nm diameter. The results, obtained by calorimetric, optical, small-angle X-ray and plasmon resonance measurements, demonstrate that a TGB_A phase, which is metastable for the pure liquid crystal host, can be effectively stabilised for a 3 K range in the presence of NPs. Moreover, the role of NPs size on the TGB_A stabilisation is briefly discussed.     

Blue phase III widening in CE6-dispersed surface-functionalised CdSe nanoparticles

The phase transition behaviour of the chiral liquid crystal CE6 doped with spherical surface-functionalised CdSe nanoparticles has been examined by means of high-resolution adiabatic scanning calorimetry and polarising microscopy. The addition of nanoparticles results in an essentially stabilised blue phase III. The phase diagram is displayed upon heating and cooling and the enthalpy changes involved in the conversion between the blue phases are determined. The dispersion of functionalised nanoparticles is prominent for the stabilisation of blue phase III, which is potentially useful for applications, especially if applied on liquid crystals that exhibit blue phases close to room temperature.     

Fluctuational electrodynamics in the presence of finite thermal sources

We present exact calculations of the spatial correlation of the blackbody radiation in the presence of spheres whose dimensions are smaller or comparable to the radiation wavelength. By going beyond the standard scalar coherence theory, we show that the spatial correlation function of a spherical thermal source is not universal but depends on the material properties of the source and exhibits near-field-induced features. Near-field effects are also manifested in the case of a linear chain of dielectric spheres where the correlation function probes the inhomogeneity of the chain. For this latter system we have established the conditions when the near-field effects cancel out and the correlation function takes the typical form of a conventional Lambertian source. For the case of a chain of metallic nanospheres, the increased spatial correlation of the far field leads to a directional thermal emission spectrum.     

New C15 Acetogenins from Two Species of Laurencia from the Aegean Sea

The chemical diversity of the approximately 1,200 natural products isolated from red algae of the genus Laurencia, in combination with the wide range of their biological activities, have placed species of Laurencia in the spotlight of marine chemists’ attention for over 60 years. The chemical investigation of the organic (CH₂Cl₂/MeOH) extracts of Laurencia microcladia and Laurencia obtusa, both collected off the coasts of Tinos island in the Aegean Sea, resulted in the isolation of 32 secondary metabolites, including 23 C₁₅ acetogenins (1–23), 7 sesquiterpenes (24–30) and 2 diterpenes (31 and 32). Among them, six new C₁₅ acetogenins, namely 10-acetyl-sagonenyne (2), cis-sagonenyne (3), trans-thuwalenyne C (4), tinosallene A (11), tinosallene B (12) and obtusallene XI (17), were identified and their structures were elucidated by extensive analysis of their spectroscopic data. Compounds 1–3, 5–11, 13 and 15–32 were evaluated for their antibacterial activity against Staphylococcus aureus and Escherichia coli.     

A Comparative Study of Various Pretreatment Approaches for Bio-Ethanol Production from Willow Sawdust,Using Co-Cultures and Mono-Cultures of Different Yeast Strains

The effect of different pretreatment approaches based on alkali (NaOH)/hydrogen peroxide (H₂O₂) on willow sawdust (WS) biomass, in terms of delignification efficiency, structural changes of lignocellulose and subsequent fermentation toward ethanol, was investigated. Bioethanol production was carried out using the conventional yeast Saccharomyces cerevisiae, as well as three non-conventional yeasts strains, i.e., Pichia stipitis, Pachysolen tannophilus, Wickerhamomyces anomalus X19, separately and in co-cultures. The experimental results showed that a two-stage pretreatment approach (NaOH (0.5% w/v) for 24 h and H₂O₂ (0.5% v/v) for 24 h) led to higher delignification (38.3 ± 0.1%) and saccharification efficiency (31.7 ± 0.3%) and higher ethanol concentration and yield. Monocultures of S. cerevisiae or W. anomalus X19 and co-cultures with P. stipitis exhibited ethanol yields in the range of 11.67 ± 0.21 to 13.81 ± 0.20 g/100 g total solids (TS). When WS was subjected to H₂O₂ (0.5% v/v) alone for 24 h, the lowest ethanol yields were observed for all yeast strains, due to the minor impact of this treatment on the main chemical and structural WS characteristics. In order to decide which is the best pretreatment approach, a detailed techno-economical assessment is needed, which will take into account the ethanol yields and the minimum processing cost.     

Design and synthesis of new C-nucleosides as potential adenosine deaminase inhibitors

A number of new pyrazolo[3,4-c] and [4,3-b]pyridine C-nucleosides, which can be viewed as 4- or 6-deazaformycin analogues were synthesized and examined as potential adenosine deaminase (ADA) inhibitors. The compounds were prepared through the condensation of a suitably substituted, lithiated 2- or 4-methylpyridine with tri-O-benzyl-d-ribonolactone, followed by borohydride reduction of the resulting hemiacetals, intramolecular Mitsunobu cyclisation of the derived diols, formation of the pyrazolopyridine ring system and subsequent removal of the protecting groups. These derivatives were designed on the structural basis provided by docking simulations performed within the enzyme catalytic site, however they demonstrated weak ADA inhibitory activity. Theoretical calculations assisted in the interpretation of the obtained biological data, thus providing guidance for rational structural modifications within this molecular scaffold.     

A general method for the synthesis of bastaranes and isobastaranes: first total synthesis of bastadins 5, 10, 12, 16, 20, and 21

A general strategy for the synthesis of twenty naturally occurring bastadins (all but bastadin 3) is presented. A key retrosynthetic disconnection of the two amide bonds, common in all target molecules, bisects the macrocyclic core into two diaryl ether fragments, an alpha,omega-diamine (western part) and an alpha,omega-dicarboxylic acid (eastern part). Efficient preparation of the synthetically challenging o-mono or dibromo-substituted diaryl ether linkages was achieved employing the diaryl iodonium salt method. Regarding the western part, variations of the aliphatic chain were more efficiently secured by the preparation of two different alpha,omega-aminonitrile moieties. Cobalt boride mediated reduction of the nitrile functionality established the required diamines and, at the same time, provided the necessary variation of the aromatic-ring bromination pattern. Regarding the eastern part, two different dicarboxyl precursors had to be prepared in order to accommodate bromination-pattern variations. Coupling and subsequent macrolactamization of different combinations of these key intermediates may lead at will to any member of this family of marine natural products. Four bastaranes (bastadins 5, 10, 12 and 16) and two isobastaranes (bastadins 20 and 21) were synthesized as a demonstration of the flexibility and efficiency of the approach presented.