Comparison of antibacterial activity of natural and hydroformylated essential oil of Thymus capitatus growing wild in north Sardinia with commercial Thymus essential oils

Thymus capitatus growing wild in Sardinia showed different essential oil composition if grown surrounding Cagliari than in north Sardinia. Here we verify the composition and antimicrobial activity of the oil to make it suitable for the cosmetic and confectionery industries. With the aim of improving the scent and the antimicrobical activity of T. capitatus essential oil, a hydroformylation reaction was carried out to transform the unsaturated components of the oil into the corresponding aldehydes. The essential oil of T. capitatus exhibited a significant antibacterial activity (MIC 0.125-0.5 mg/mL), and was also found effective on C. albicans (MIC 0.125 mg/mL). After hydroformylation, several new irregular terpenoid aldehydes were detected. The perfume of the new terpenic-like aldehydes is very agreeable and, therefore, the acceptability of the aroma is remarkably improved, but the antimicrobial activity was not increased.     

Ramsey-type spectroscopy with high-order harmonics

We present an experiment where Ramsey-type spectroscopy is applied to autoionizing states of krypton by using the ninth harmonic (88 nm) of a femtosecond Ti:sapphire laser. The ionization process, detected by an electron-energy spectrometer, shows the characteristic quantum interference pattern. The behavior of the fringe contrast compares favorably with a simple essential-state model, whose parameters have been taken from the literature. The experiment shows the feasibility of high-resolution spectroscopy in the extreme ultraviolet by using high-order laser harmonics.     

The occurrence of iridoid glycosides in Cymbalaria spp. in Italy

The occurrence of iridoid glycosides in a number of Cymbalaria spp. collected in Italy is shown and chemosystematic implications are discussed.     

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.