Chemical Characterization and Bioactivity of Commercial Essential Oils and Hydrolates Obtained from Portuguese Forest Logging and Thinning

Essential oils (EOs) and hydrolates (Hds) are natural sources of biologically active ingredients with broad applications in the cosmetic industry. In this study, nationally produced (mainland Portugal and Azores archipelago) EOs (11) and Hds (7) obtained from forest logging and thinning of Eucalyptus globulus, Pinus pinaster, Pinus pinea and Cryptomeria japonica, were chemically evaluated, and their bioactivity and sensorial properties were assessed. EOs and Hd volatiles (HdVs) were analyzed by GC-FID and GC-MS. 1,8-Cineole was dominant in E. globulus EOs and HdVs, and α- and β-pinene in P. pinaster EOs. Limonene and α-pinene led in P. pinea and C. japonica EOs, respectively. P. pinaster and C. japonica HVs were dominated by α-terpineol and terpinen-4-ol, respectively. The antioxidant activity was determined by DPPH, ORAC and ROS. C. japonica EO showed the highest antioxidant activity, whereas one of the E. globulus EOs showed the lowest. Antimicrobial activity results revealed different levels of efficacy for Eucalyptus and Pinus EOs while C. japonica EO showed no antimicrobial activity against the selected strains. The perception and applicability of emulsions with 0.5% of EOs were evaluated through an in vivo sensory study. C. japonica emulsion, which has a fresh and earthy odour, was chosen as the most pleasant fragrance (60%), followed by P. pinea emulsion (53%). In summary, some of the studied EOs and Hds showed antioxidant and antimicrobial activities and they are possible candidates to address the consumers demand for more sustainable and responsibly sourced ingredients.     

Vibrational overtone spectroscopy of three-membered rings

We have recorded vapor-phase photoacoustic spectra of cyclopropane, ethylene oxide, and ethylene sulfide in the third, fourth, and fifth CH-stretching overtone regions. We have used a harmonically coupled anharmonic oscillator local mode model to facilitate analysis of the spectra. Fermi resonance between the CH-stretching and HCH-bending vibrations is essential to explain the observed wide and multistructured CH-stretching overtone bands. A number of weak combination bands can account for the remaining experimental features observed to the blue of the CH-stretching regions. We have reassigned the fundamental spectra of these three-membered rings.     

EPR spectroscopy of protein microcrystals oriented in a liquid crystalline polymer medium

Correlation of the g-tensor of a paramagnetic active center of a protein with its structure provides a unique experimental information on the electronic structure of the metal site. To address this problem, we made solid films containing metalloprotein (Desulfovibrio gigas cytochrome c(3)) microcrystals. The microcrystals in a liquid crystalline polymer medium (water/hydroxypropylcellulose) were partially aligned by a shear flow. A strong orientation effect of the metalloprotein was observed by EPR spectroscopy and polarizing optical microscopy. The EPR spectra of partially oriented samples were simulated, allowing for molecular orientation distribution function determination. The observed effect results in enhanced sensitivity and resolution of the EPR spectra and provides a new approach towards the correlation of spectroscopic data, obtained by EPR or some other technique, with the three-dimensional structure of a protein or a model compound.     

A suppression strategy for antibiotic discovery

High-throughput phenotype screening and target identification have been combined in an effort to isolate antimicrobial, small-molecule therapeutics. This approach, developed by Brown and colleagues and reported in this issue, is a major technological advance for antimicrobial drug discovery.     

Optimized pathway selection in intraresidual triple-resonance experiments

An optimized intraresidual pulse sequence element with better sensitivity and suppression of sequential cross peaks is presented. Concatenation of three magnetization transfer delays allows their independent setting, in accordance with the relaxation properties of the individual spins, without concomitantly prolonging the pulse sequence. Additionally, implementations of the scheme to HNCA, HNCACB, and the TROSY based triple-resonance experiments are proposed. The feasibility of the new element was verified by recording HNCA and HNCACB on the small 8.6 kDa protein ubiquitin. The corresponding HNCA-TROSY experiment was tested on a larger protein, the 30.4 kDa Cel6A from the thermophilic soil bacterium Thermobifida fusca at 800 (1)H MHz.     

7 T versus 3 T contrast-enhanced breast Magnetic Resonance Imaging of invasive ductulolobular carcinoma: First clinical experience

Purpose

Here we describe our first experience with contrast-enhanced (CE) MRI of breast cancer at 7 tesla (T), compared to 3 T and histopathology.

Materials and Methods

A 52 year old female patient with a mammographically suspicious breast mass (BI-RADS V) underwent 7 T CE-MRI. Results were described according to the BI-RADS-MRI criteria and compared to 3 T and histopathology.

Results

After contrast administration, a homogeneously enhancing, irregular spiculated mass was depicted at both 3 T and 7 T; sizes were identical. The most malignant kinetic curve was characterized by a rapid initial rise followed by a wash-out pattern in the delayed phase, i.e. a type 3 curve, at both field strengths. Even though T1-effects of contrast agents are suggested to be reduced at higher fields, quantification of contrast enhancement-to-noise ratio showed a ratio of 4.6 at 7 T and 2.8 at 3 T when comparing contrast-to-noise of the mass before and after contrast administration. Both examinations, using a single dose of gadolinium-based contrast agent, achieved good image quality. Final histopathological evaluation showed an invasive ductulolobular carcinoma with an intraductal component.

Conclusion

This initial experience suggests that clinical contrast-enhanced 7 T MRI of the breast is technically feasible and may allow BI-RADS-conform analysis.     

Properties and processing of cork powder filled cellulose derivatives composites

This paper deals with the use of cork powder, a by‐product from cork industry, as a filler to reinforce hydroxypropyl cellulose (HPC) matrix. Several films were prepared using HPC, as a matrix, filled with different amounts of cork powder (average diameter < 50 μm) (0.0; 0.5; 1.0 and 10.0% w/w) and in the presence or not of 1,4‐diisocyanatobutane (BDI) (7.0% w/w). Before the elaboration of these films, the surface properties of cork powder as well as that of suberin (main component of cork) were determined by Inverse Gas Chromatography (IGC). The tensile properties of the solid films obtained were studied and, as expected, for the films with BDI but without cork powder, the Young's modulus and the tensile strength increased, while the elongation decreased. However with the filled films it seemed that the Young's modulus decreased and the elongation increased. The Scanning Electron Microscopy showed that the fractured plane of samples with cross‐linking agent and cork powder displayed some nucleation points (0.3 μm) which indicates a strongly bonded interface and which could be considered as a responsible for the high mechanical properties observed.     

Molecular Modeling Approaches Can Reveal the Molecular Interactions Established between a Biofilm and the Bioactive Compounds of the Essential Oil of Piper divaricatum

Molecular modeling approaches are used in a versatile way to investigate the properties of diverse organic and inorganic structures such as proteins, biomolecules, nanomaterials, functionalized nanoparticles, and membranes. However, more detailed studies are needed to understand the molecular nature of interactions established in gelatin biofilms impregnated with bioactive compounds. Because of this, we used computational methods to evaluate how the major compounds of Piper divaricatum essential oil can interact with the gelatin biofilm structure. For this, we used as inspiration the paper published, where various properties of the essential oil impregnated gelatin biofilm P. divaricatum are reported. After our computer simulations, we related our molecular observations to biofilm’s structural and mechanical properties. Our results suggest that the major compounds of the essential oil were able to interrupt intermolecular interactions between the chains of the biofilm matrix. However, the compounds also established interactions with the amino acid residues of these chains. Our molecular analyses also explain changes in the structural and mechanical properties of the essential oil-impregnated biofilm. These results can support the planning of functional packaging impregnated with bioactive compounds that can protect food against microorganisms harmful to human health.     

Ruthenium-catalyzed asymmetric transfer hydrogenation of ketones in ethanol

A ruthenium catalyst formed in situ by combining [Ru(p-cymene)Cl₂]₂ and an amino acid hydroxy-amide was found to catalyze efficiently the asymmetric reduction of aryl alkyl ketones under transfer hydrogenation conditions using ethanol as the hydrogen donor. The secondary alcohol products were obtained in moderate to good yields and with good to excellent enantioselectivity (up to 97% ee).