Within-Plant Variation in Rosmarinus officinalis L. Terpenes and Phenols and Their Antimicrobial Activity against the Rosemary Phytopathogens Alternaria alternata and Pseudomonas viridiflava

This study investigated within-plant variability of the main bioactive compounds in rosemary (Rosmarinus officinalis L.). Volatile terpenes, including the enantiomeric distribution of monoterpenes, and phenols were analyzed in young and mature foliar, cortical and xylem tissues. In addition, antimicrobial activity of rosmarinic acid and selected terpenes was evaluated against two rosemary pathogens, Alternaria alternata and Pseudomonas viridiflava. Data showed that total concentration and relative contents of terpenes changed in relation to tissue source and age. Their highest total concentration was observed in the young leaves, followed by mature leaves, cortical and xylem tissues. Rosmarinic acid and carnosic acid contents did not show significant differences between leaf tissues of different ages, while young and mature samples showed variations in the content of four flavonoids. These results are useful for a more targeted harvesting of rosemary plants, in order to produce high-quality essential oils and phenolic extracts. Microbial tests showed that several terpenes and rosmarinic acid significantly inhibited the growth of typical rosemary pathogens. Overall, results on antimicrobial activity suggest the potential application of these natural compounds as biochemical markers in breeding programs aimed to select new chemotypes less susceptible to pathogen attacks, and as eco-friendly chemical alternatives to synthetic pesticides.     

Flavonoids in Lemon and Grapefruit IntegroPectin**

Following the analysis of terpenes present in new lemon and grapefruit “IntegroPectin” pectins obtained via the hydrodynamic cavitation of industrial lemon and grapefruit processing waste, the HPLC-MS analysis of flavonoid and other phenolic compounds reveals the presence of eriocitrin, naringin, hesperidin and kaempferol typical of the respective citrus fruits. The pectic fibers rich in rhamnogalacturonan-I regions act as chemical sponges adsorbing and concentrating at their outer surface highly bioactive citrus flavonoids and terpenes. These findings, together with the unique molecular structure of these new whole citrus pectins, provide preliminary insight into the broad-scope biological activity of these new biomaterials. Numerous new biomedical applications are anticipated, including likely use in the prevention and treatment of microbial infections and neurodegenerative disease.     

A Stimuli‐Responsive Rotaxane–Gold Catalyst: Regulation of Activity and Diastereoselectivity

A rotaxane‐based Au catalyst was developed and the effect of the mechanical bond on its behavior was studied. Unlike the non‐interlocked thread, the rotaxane requires a catalytically innocent cofactor, the identity of which significantly influences both the yield and diastereoselectivity of the reaction. Under optimized conditions, Au^I (the catalyst), Ag^I (to abstract the Cl^? ligand), and Cu^I (the cofactor) combine to produce a catalyst with excellent activity and selectivity.     

Transformations of benzothiadiphosphole system: General one‐pot synthesis of 1,2,5‐dithiaphosphepines and their precursor phosphanethiols

Treatment, at room temperature, of benzothiadiphosphole 1 with BrMg(CH₂)₅MgBr gives intermediate A , which was allowed to stand for about 3 h at room temperature. The subsequent addition of RMgX to the reaction mixture and the final treatment with an excess of S₈ and water affords the dithiaphosphepine sulfide 8 in good yields. The structure of this new heterocyclic system, containing both an S S unit and a PS group, is confirmed by an single crystal X‐ray structure determination. If the reaction is carried out without final treatment with sulfur we obtain, using PhMgBr as mono‐Grignard reagent, the corresponding ring‐opened product 11b , which can be easily transformed into the corresponding ring‐opened sulfide 12b by simple treatment with elemental sulfur. Further addition of sulfur to 12b gives quantitatively the cyclic dithiaphosphepine sulfide 8b . The two phosphanethiols 11b and 12b are of considerable interest. In fact, recently, attention has increasingly been paid to the coordination chemistry of polydentate ligands incorporating both thiolate and tertiary phosphine groups, also known as S P S pincer ligands. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:339–345, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20099     

A Zinc-Mediated Deprotective Annulation Approach to New Polycyclic Heterocycles

A straightforward approach to new polycyclic heterocycles, 1H-benzo[4,5]imidazo[1,2-c][1,3]oxazin-1-ones, is presented. It is based on the ZnCl₂-promoted deprotective 6-endo-dig heterocyclization of N-Boc-2-alkynylbenzimidazoles under mild conditions (CH₂Cl₂, 40 °C for 3 h). The zinc center plays a dual role, as it promotes Boc deprotection (with formation of the tert-butyl carbocation, which can be trapped by substrates bearing a nucleophilic group) and activates the triple bond toward intramolecular nucleophilic attack by the carbamate group. The structure of representative products has been confirmed by X-ray diffraction analysis.     

Amperometric Sniffer Based on Electrodes Supported on Ion‐Exchangers for Monitoring the State of Turning Rancid of Lipids

A porous gold electrode supported on one face of an ion‐exchange membrane, acting as a solid polymer electrolyte (SPE), is proposed as an amperometric sniffer for monitoring the aldehyde content in the headspace in equilibrium with lipid samples, in order to gain indication of their state of turning rancid It was used as a detector for a flow injection system in which aldehydes were injected, after preconcentration by solid phase microextraction on a SPME fiber from the gas phase standing above thermostated samples and subsequent desorption by heating. Repeatable (±4.5%) sharp peaks were detected over a wide linear concentration range (0.5–200 ppm). A detection limit of about 0.03 ppm was inferred for a signal‐to‐noise ratio of 3, referred to hexylaldehyde (used as prototype) dissolved in squalene or vegetable oils samples. This approach was applied to the determination of volatile aldehydes from some partially oxidized cereal oils and the results found were compared with both the corresponding peroxide values and their aldehyde content determined by a conventional spectrophotometric method.     

Combined use of X-ray photoelectron and Mössbauer spectroscopic techniques in the analytical characterization of iron oxidation state in amphibole asbestos

Asbestos fibers are an important cause of serious health problems and respiratory diseases. The presence, structural coordination, and oxidation state of iron at the fiber surface are potentially important for the biological effects of asbestos because iron can catalyze the Haber–Weiss reaction, generating the reactive oxygen species ?OH. Literature results indicate that the surface concentration of Fe(III) may play an important role in fiber-related radical formation. Amphibole asbestos were analyzed by X-ray photoelectron spectroscopy (XPS) and Mössbauer spectroscopy, with the aim of determining the surface vs. bulk Fe(III)/Fe_tot ratios. A standard reference asbestos (Union Internationale Contre le Cancer crocidolite from South Africa) and three fibrous tremolite samples (from Italy and USA) were investigated. In addition to the Mössbauer spectroscopy study of bulk Fe(III)/Fe_tot ratios, much work was dedicated to the interpretation of the XPS Fe2p signal and to the quantification of surface Fe(III)/Fe_tot ratios. Results confirmed the importance of surface properties because this showed that fiber surfaces are always more oxidized than the bulk and that Fe(III) is present as oxide and oxyhydroxide species. Notably, the highest difference of surface/bulk Fe oxidation was found for San Mango tremolite—the sample that in preliminary cytotoxicity tests (MTT assay) had revealed a cell mortality delayed with respect to the other samples.     

Some alternative methods for hydrodynamic closures to dissipative kinetic models

Two different strategies for deriving hydrodynamic equations for dissipative kinetic models are presented and discussed. The homogeneity scaling approach, not very well-known in the physical literature, is expanded and applied to different show-cases in several applications. Then, we show that this strategy may fail, as it occurs for a thermalized granular gas in a host medium, in which case the problem can be dealt with by resorting to classical moment closure methods.     

Multi-temperature Hydrodynamic Limit from Kinetic Theory in a Mixture of Rarefied Gases

Starting from the Boltzmann kinetic equations for a mixture of gas molecules whose internal structure is described by a discrete set of internal energy levels, hydrodynamic equations at Euler level are deduced by a consistent hydrodynamic limit in the presence of a two-scale collision process. The fast process driving evolution is constituted by mechanical encounters between particles of the same species, whereas inter-species scattering proceeds at the macroscopic scale. The resulting multi-temperature and multi-velocity fluid-dynamic equations are briefly commented on, and some results in closed analytical form are given for special simplified situations like Maxwellian collision kernels, or mono-atomic hard sphere gases.     

A new method for microcapsule characterization

Numerous microcapsule systems have been developed for a wide range of applications, including the sustained release of drugs, cell transplantation for therapy, cell immobilization, and other biotechnological applications. Despite the fact that microcapsule membrane is a dominant factor governing overall microcapsule performance, its characterization is challenging. We report a new method for characterizing microcapsule membranes, using the most common alginate-poly-l-lysine-alginate (APA) microcapsule as an example. Our data demonstrate that genipin, a naturally derived reagent extracted from gardenia fruits, interacts with poly-l-lysine (PLL) and generates fluorescence. This fluorescence allows clear visualization and easy analysis of the PLL membrane in the APA microcapsules using confocal laser scanning microscopy. The results also show that PLL binding correlates to the reaction variables during PLL coating such as PLL concentration and coating time. In addition, five other different microcapsule formulations consisting of PLL and/or chitosan membranes were examined, and the results imply that this method can be extended to characterize a variety of microcapsule membranes. These findings suggest that genipin can serve as a fluorogenic marker for rapid characterization of microcapsule membranes, a superior method that would have important implications for microcapsule research and potential in many other applications.