Synthesis of new chiral organosulfur donors with hydrogen bonding functionality and their first charge transfer salts

The syntheses of a range of enantiopure organosulfur donors with hydrogen bonding groups are described including TTF related materials with two, four, six and eight hydroxyl groups and multiple stereogenic centres and a pair of chiral N-substituted BEDT-TTF acetamides. Three charge transfer salts of enantiopure poly-hydroxy-substituted donors are reported, including a 4:1 salt with the meso stereoisomer of the dinuclear [Fe2(oxalate)5 ]4- anion in which both cation and anion have chiral components linked together by hydrogen bonding, and a semiconducting salt with triiodide

Altered distribution of mucosal NK cells during HIV infection.

The human gut mucosa is a major site of human immunodeficiency virus (HIV) infection and infection-associated pathogenesis. Increasing evidence shows that natural killer (NK) cells have an important role in control of HIV infection, but the mechanism(s) by which they mediate antiviral activity in the gut is unclear. Here, we show that two distinct subsets of NK cells exist in the gut, one localized to intraepithelial spaces (intraepithelial lymphocytes, IELs) and the other to the lamina propria (LP). The frequency of both subsets of NK cells was reduced in chronic infection, whereas IEL NK cells remained stable in spontaneous controllers with protective killer immunoglobulin-like receptor/human leukocyte antigen genotypes. Both IEL and LP NK cells were significantly expanded in immunological non-responsive patients, who incompletely recovered CD4+ T cells on highly active antiretroviral therapy (HAART). These data suggest that both IEL and LP NK cells may expand in the gut in an effort to compensate for compromised CD4+ T-cell recovery, but that only IEL NK cells may be involved in providing durable control of HIV in the gut

Phytochemistry and pharmacology of the genus Drypetes: A review

Aims: Traditional medicinal use of species of the genus Drypetes is widespread in the tropical regions. The aim of this review is to systematically appraise the literature available to date on phytochemistry, ethnopharmacology, toxicology and bioactivity (in vitro and in vivo) of crude extracts and purified compounds. Ethnopharmacological relevance: Plants of the genus Drypetes (Putranjivaceae) are used in the Subsaharan African and Asian traditional medicines to treat a multitude of disorders, like dysentery, gonorrhoea, malaria, rheumatism, sinusitis, tumours, as well as for the treatment of wounds, headache, urethral problems, fever in young children, typhoid and several other ailments. Some Drypetes species are used to protect food against pests, as an aphrodisiac, a stimulant/depressant, a rodenticide and a fish poison, against insect bites, to induce conception and for general healing. This review deals with updated information on the ethnobotany, phytochemistry, and biological activities of ethnomedicinally important Drypetes species, in order to provide an input for the future research opportunities. Methods: An extensive review of the literature available in various recognized databases e.g., Google Scholar, PubMed, Science Direct, SciFinder, Web of Science, www.theplantlist.org and www.gbif.org, as well as the Herbier National du Cameroun (Yaoundé) and Botanic Gardens of Limbe databases on the uses and bioactivity of various species of the Drypetes was undertaken. Results: The literature provided information on ethnopharmacological uses of the Subsaharan African and Asian species of the genus Drypetes, e.g., Drypetes aubrévillii, D. capillipes, D. chevalieri, D. gerrardii, D. gossweileri, D. ivorensis, D. klainei, D. natalensis, D. pellegrini (all endemic to Africa) and D. roxburghii (Asian species), for the treatment of multiple disorders. From a total of 19 species, more than 140 compounds including diterpenes, sesquiterpenes, triterpenes (friedelane, oleanane, lupane and hopane-type), flavonoids, lignans, phenylpropanoids and steroids, as well as some thiocyanates, were isolated. Several crude extracts of these plants, and isolated compounds displayed significant analgesic, anthelmintic, antidiabetic, anti-emetic anti-inflammatory, antioxidant, antiparasitic, central nervous system depressant, cytotoxic, and insecticidal activities both in vitro and in vivo. Some toxicities associated with the stem, bark, seed and leaf extracts of D. roxburghii, and the flavonoid, amentoflavone, isolated from the stem extract of D. littoralis as well as D. gerrardii, were confirmed in the animal models and in the rat skeletal myoblast cells assays. As a consequence, traditional medicine from this genus should in future be applied with care. Conclusions: Plants of this genus have offered bioactive samples, both from crude extracts and pure compounds, partly validating their effectivity in traditional medicine. However, most of the available scientific litteratures lacks information on relevant doses, duration of the treatment, storage conditions and positive controls for examining bioefficacy of extract and its active compounds. Additional toxicological studies on the species used in local pharmacopeia are urgently needed to guarantee safe application due to higth toxicity of some crude extracts. Interestingly, this review also reports 10 pimarane dinorditerpenoids structures with the aromatic ring C, isolated from the species collected in Asia Drypetes littoralis (Taiwan), D. perreticulata (China), and in Africa D. gerrardii (Kenya), D. gossweileri (Cameroon). These compounds might turn out to be good candidates for chemotaxonomic markers of the genus

Charge transfer complexes and radical cation salts of chiral methylated organosulfur donors

The single crystal X-ray structure of the all-axial conformer of the (R,R,R,R) enantiomer of the chiral donor tetramethyl-BEDT-TTF (TM-BEDT-TTF) was described and compared to the all-equatorial conformer. (S,S,S,S)-Tetramethyl-BEDT-TTF formed crystalline 1 : 1 complexes with TCNQ and TCNQ-F4, as well as a THF solvate of the TCNQ complex. Donors bis((2S,4S)-pentane-2,4-dithio)tetrathiafulvalene and (ethylenedithio)((2S,4S)-pentane-2,4-dithio)tetrathiafulvalene, which contain seven-membered rings bearing chirally oriented methyl groups, only formed complexes with TCNQ-F4. The TCNQ-F4 complexes contain planar organosulfur systems, in contrast to the TCNQ complexes in which there is minimal charge transfer. A variety of crystal packing modes were observed. Electrocrystallization experiments with both enantiomers and the racemic form of tetramethyl-BEDT-TTF afforded mixed valence radical cation salts with the AsF6 and SbF6 anions formulated as (TM-BEDT-TTF)2XF6 (X = As, Sb). Electrical conductivity was only found in one charge transfer complex, while the radical cation salts are all semiconducting

Facile one-pot synthesis of amoxicillin-coated gold nanoparticles and their antimicrobial activity

Nanomaterials have been the object of intense study due to promising applications in a number of different disciplines. In particular, medicine and biology have seen the potential of these novel materials with their nanoscale properties for use in diverse areas such as imaging, sensing and drug vectorisation. Gold nanoparticles (GNPs) are considered a very useful platform to create a valid and efficient drug delivery/carrier system due to their facile and well-studied synthesis, easy surface functionalization and biocompatibility. In the present study, stable antibiotic conjugated GNPs were synthesised by a one-step reaction using a poorly water soluble antibiotic, amoxicillin. Amoxicillin, a member of the penicillin family, reduces the chloroauric acid to form nanoparticles and at the same time coats them to afford the functionalised nanomaterial. A range of techniques including UV-vis spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) were used to ascertain the gold/drug molar ratio and the optimum temperature for synthesis of uniform monodisperse particles in the ca. 30-40 nm size range. Amoxicillin-conjugated gold showed an enhancement of antibacterial activity against Escherichia coli compared to the antibiotic alone

A novel instrument to measure differential ablation of meteorite samples and proxies: The Meteoric Ablation Simulator (MASI)

On entering the Earth’s atmosphere, micrometeoroids partially or completely ablate, leaving behind layers of metallic atoms and ions. The relative concentration of the various metal layers is not well explained by current models of ablation. Furthermore, estimates of the total flux of cosmic dust and meteoroids entering the Earth’s atmosphere vary over two orders of magnitude. To better constrain these estimates and to better model the metal layers in the mesosphere, an experimental meteoric Ablation Simulator (MASI) has been developed. Interplanetary Dust Particle (IDP) analogs are subjected to temperature profiles simulating realistic entry heating, to ascertain the differential ablation of relevant metal species. MASI is the first ablation experiment capable of simulating detailed mass, velocity, and entry angle-specific temperature profiles whilst simultaneously tracking the resulting gas-phase ablation products in a time resolved manner. This enables the determination of elemental atmospheric entry yields which consider the mass and size distribution of IDPs. The instrument has also enabled the first direct measurements of differential ablation in a laboratory setting

On the Mechanistic Origins of Toughness in Bone

One of the most intriguing protein materials found in nature is bone, a material composed of assemblies of tropocollagen molecules and tiny hydroxyapatite mineral crystals that form an extremely tough, yet lightweight, adaptive and multifunctional material. Bone has evolved to provide structural support to organisms, and therefore its mechanical properties are of great physiological relevance. In this article, we review the structure and properties of bone, focusing on mechanical deformation and fracture behavior from the perspective of the multidimensional hierarchical nature of its structure. In fact, bone derives its resistance to fracture with a multitude of deformation and toughening mechanisms at many size scales ranging from the nanoscale structure of its protein molecules to the macroscopic physiological scale.United States. Army Research Office (contract number W911NF-06-1-0291)National Science Foundation (U.S.) (CAREER award (contract number 0642545))Lawrence Berkeley National Laboratory (Laboratory Directed Research and Development Program)United States. Dept. of Energy (Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, contract number DE-AC02-05CH11231

Web Service Discovery in a Semantically Extended UDDI Registry: the Case of FUSION

Service-oriented computing is being adopted at an unprecedented rate, making the effectiveness of automated service discovery an increasingly important challenge. UDDI has emerged as a de facto industry standard and fundamental building block within SOA infrastructures. Nevertheless, conventional UDDI registries lack means to provide unambiguous, semantically rich representations of Web service capabilities, and the logic inference power required for facilitating automated service discovery. To overcome this important limitation, a number of approaches have been proposed towards augmenting Web service discovery with semantics. This paper discusses the benefits of semantically extending Web service descriptions and UDDI registries, and presents an overview of the approach put forward in project FUSION, towards semantically-enhanced publication and discovery of services based on SAWSDL

Cytotoxic properties of the stem bark of Citrus reticulata Blanco (Rutaceae)

The bioassay-guided fractionation of the n-hexane extract of Citrus reticulata Blanco (Rutaceae) stem bark yielded scoparone (1), xanthyletin (2), lupeol (3), β-amyrin (4), stigmasterol (5), β-sitosterol (6) and palmitic acid. The structures of these compounds were determined by comprehensive spectroscopic analyses, i.e., 1D and 2D NMR and EI-MS, and by comparison with the reported data. Extracts, fractions and isolated compounds 1-6 were assessed for cytotoxicity by the MTT assay against three human cancer cell lines, i.e., human lung adenocarcinoma cell line A549, human breast adenocarcinoma cell line MCF7 and human Caucasian prostate adenocarcinoma cell line PC3. Significant activity of the n-hexane and the dichloromethane extracts was observed against the breast cancer cell line MCF7 with IC50s of 45.6 and 54.7 μg/mL, respectively. Moreover, the 70% ethyl acetate in n-hexane chromatographic fraction showed significant activity displaying IC50 values of 53.0, 52.4 and 49.1 μg/mL against the cancer cell lines A549, MCF7 and PC3, respectively. Encouragingly, an IC50 of 510.0 µg/mL against the human normal prostate cell line PNT2 indicated very low toxicity, and hence favourable selectivity indices for the 70% ethyl acetate in n-hexane fraction in the range of 9.6-10.4 towards cell lines A549, MCF7 and PC3. Since compounds isolated from the above fraction only delivered IC50 values in the range of 18.2-96.3, 9.2-34.1 and 7.5-97.2 μg/mL against A549, MCF7 and PC3 cell lines, respectively, synergistic action between compounds is suggested. Bioassay results valorize the anticancer effectivity of the stem bark of this plant in Cameroonian pharmacopeia

Phylogeny of Prokaryotes and Chloroplasts Revealed by a Simple Composition Approach on All Protein Sequences from Complete Genomes Without Sequence Alignment

The complete genomes of living organisms have provided much information on their phylogenetic relationships. Similarly, the complete genomes of chloroplasts have helped to resolve the evolution of this organelle in photosynthetic eukaryotes. In this paper we propose an alternative method of phylogenetic analysis using compositional statistics for all protein sequences from complete genomes. This new method is conceptually simpler than and computationally as fast as the one proposed by Qi et al. (2004b) and Chu et al. (2004). The same data sets used in Qi et al. (2004b) and Chu et al. (2004) are analyzed using the new method. Our distance-based phylogenic tree of the 109 prokaryotes and eukaryotes agrees with the biologists tree of life based on 16S rRNA comparison in a predominant majority of basic branching and most lower taxa. Our phylogenetic analysis also shows that the chloroplast genomes are separated to two major clades corresponding to chlorophytes s.l. and rhodophytes s.l. The interrelationships among the chloroplasts are largely in agreement with the current understanding on chloroplast evolution