Red clover (Trifolium pratense L.) isoflavones: determination of concentrations by plant stage,flower colour,plant part and cultivar

BACKGROUND: Red clover (Trifolium pratense L.), a widely used fodder, has recently received considerable interest as a valuable source of isoflavones for many health‐related applications. The aim of this study was to analyse the concentrations of four isoflavones, daidzein, genistein, formononetin and biochanin A, in extracts of leaves, stems, roots and different coloured flowers from red clover by high‐performance liquid chromatography and to determine the antifungal activities of the extracts. RESULTS: Among greenhouse‐grown samples the highest amounts of daidzein and genistein were found in petioles (0.11–0.28 and 0.30–0.54 mg g^?1 respectively), while leaves were rich in formononetin and biochanin A (5.57–9.05 and 10.94–14.59 mg g^?1 respectively). High formononetin concentrations were found in roots, but very little biochanin A. Among field‐grown samples the highest concentrations of daidzein and genistein were detected in stems collected in August (0.24 and 0.55 mg g^?1 respectively), while the highest amounts of formononetin and biochanin A were found in young leaves collected in June (7.47 and 9.69 mg g^?1 respectively). Most of the extracts inhibited the growth of Drechslera teres, while the root extract showed the strongest effect against Microdochium nivale. CONCLUSION: High levels of bioactive compounds found not only in inflorescences but also in roots, leaves and stems suggest that red clover may be an inexpensive and valuable resource for many applications. Copyright © 2007 Society of Chemical Industry     

Environmental Control of Triplet Emission in Donor–Bridge–Acceptor Organometallics

Carbene‐metal‐amides (CMAs) are a promising family of donor–bridge–acceptor molecular charge‐transfer (CT) emitters for organic light‐emitting diodes. A universal approach is demonstrated to tune the energy of their CT emission. A blueshift of up to 210 meV is achievable in solid state via dilution in a polar host matrix. The origin of this shift has two components: constraint of thermally‐activated triplet diffusion, and electrostatic interactions between guest and polar host. This allows the emission of mid‐green CMA archetypes to be tuned to sky blue without chemical modifications. Monte‐Carlo simulations based on a Marcus‐type transfer integral successfully reproduce the concentration‐ and temperature‐dependent triplet diffusion process, revealing a substantial shift in the ensemble density of states in polar hosts. In gold‐bridged CMAs, this shift does not lead to a significant change in luminescence lifetime, thermal activation energy, reorganization energy, or intersystem crossing rate. These discoveries offer new insight into coupling between the singlet and triplet manifolds in CMA materials, revealing a dominant interaction between states of CT character. The same approach is employed using materials which have been chemically modified to alter the energy of their CT state directly, shifting the emission of sky‐blue chromophores into the practical blue range.     

Friction and a Tribochemical Reaction between Ice and Hexagonal Boron Nitride: A Theoretical Study

Friction between ice-Ih and hexagonal boron nitride (h-BN) has been determined by periodic ab initio calculations. Surfaces of ice-Ih and h-BN were brought into sliding contact, and the interaction energies were calculated as a function of interplanar distance and lateral displacement of the surfaces. The friction between the surfaces was calculated from the interaction energies, producing a friction coefficient of 0.140. Friction is further influenced at high loads by a tribochemical reaction between ice-Ih and h-BN.     

Characterization of biodegradable core–clad borosilicate glass fibers with round and rectangular cross-section

Here, we report on core–clad bioactive borosilicate fibers, that we have prepared both with round and rectangular cross-section profile. The exposed approach, which relies on the stacking and drawing of glass slabs, demonstrates our ability to develop bioactive-based glass fibers with tailored cross-section profiles. Tens-of-meters-long fibers were successfully drawn, although suffering from elevated losses in the case of the rectangular ones. The response of the fibers in simulated body fluid was studied for both geometries. We found that a round cladding can act as protective layer, tempering effects of the corrosion. We also noticed that rectangular fibers are more prone to degradation, the enhanced corrosion beginning from their sharp corners as they accumulated residual tensile stress during drawing. To the best of our knowledge, this is the first report on the effect of residual tensile stresses from surface tension deformations applied to the corrosion of rectangular fibers. As geometry plays a critical role on the biodegradation behavior of the fiberglass, we believe the enclosed results could lead to the design of fiber devices with tailored cross-section profile in order to tune their rate of degradation on solely based geometrical effects.     

The ELPI Response and Data Reduction II: Properties of Kernels and Data Inversion

The first part of this article reports the analytical form of the Electrical Low Pressure Impactor (ELPI) kernel functions. In this latter part, the numerical quality of ELPI response matrices is studied and an example of an inversion algorithm is given. The ELPI assemblies with and without an electrical filter stage and with smooth or sintered impaction plates are studied and compared with basic impactor kernels and the kernels for the calculation of the aerosol mass distribution. It is shown that the ELPI assembly with the electrical filter stage and smooth impaction plates should be the best choice for the inversion of data if no bounce occurs. The comparison to a mass impactor shows that the devices are on par in data inversion. The inversion ELPI data is studied with a Bayesian algorithm assuming a bimodal lognormal size distribution of the aerosol. The algorithm includes a novel procedure for obtaining an initial guess of the distribution parameters. To our knowledge, it is also the first algorithm to use ELPI current readings as its input. Simulations and diesel emission measurements show that the proposed algorithm is a useful tool in the study of ELPI data.     

Toxicological characterization of particulate emissions from straw,Miscanthus, and poplar pellet combustion in residential boilers

Wood pellets have been used in domestic heating appliances for three decades. However, because the share of renewable energy for heating will likely rise over the next several years, alternative biomass fuels, such as short-rotation coppice or energy crops, will be utilized. We tested particulate emissions from the combustion of standard softwood pellets and three alternative pellets (poplar, Miscanthus sp., and wheat straw) for their ability to induce inflammatory, cytotoxic, and genotoxic responses in a mouse macrophage cell line. Our results showed clear differences in the chemical composition of the emissions, which was reflected in the toxicological effects. Standard softwood and straw pellet combustion resulted in the lowest PM₁ mass emissions. Miscanthus sp. and poplar combustion emissions were approximately three times higher. Emissions from the herbaceous biomass pellets contained higher amounts of chloride and organic carbon than the emissions from standard softwood pellet combustion. Additionally, the emissions of the poplar pellet combustion contained the highest concentration of metals. The emissions from the biomass alternatives caused significantly higher genotoxicity than the emissions from the standard softwood pellets. Moreover, straw pellet emissions caused higher inflammation than the other samples. Regarding cytotoxicity, the differences between the samples were smaller. Relative toxicity was generally highest for the poplar and Miscanthus sp. samples, as their emission factors were much higher. Thus, in addition to possible technical problems, alternative pellet materials may cause higher emissions and toxicity. The long-term use of alternative fuels in residential-scale appliances will require technological developments in both burners and filtration.

Copyright © 2016 American Association for Aerosol Research     

Failure mechanism of thin Al2O3 coatings grown by atomic layer deposition for corrosion protection of carbon steel

Combined analysis by electrochemical impedance spectroscopy (EIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and field emission scanning electron microscopy (FESEM) of the corrosion protection provided to carbon steel by thin (50 nm) Al₂O₃ coatings grown by atomic layer deposition (ALD) and its failure mechanism is reported. In spite of excellent sealing properties, the results show an average dissolution rate of the alumina coating of ∼7 nm h⁻¹ in neutral 0.2 M NaCl and increasing porosity of the remaining layers with increasing immersion time. Alumina dissolution is triggered by the penetration of the solution via cracks/pinholes through the coating to the substrate surface where oxygen reduction takes place, raising the pH. At defective substrate surface sites of high aspect ratio and concentrated residual mechanical stress (along scratches) presumably exposing a higher steel surface fraction, localized dissolution of the coating is promoted by a more facile access of the solution to the substrate surface enhancing oxygen reduction. De-adhesion of the coating is also promoted in these sites by the ingress of the anodic dissolution trenching the steel surface. Localized corrosion of the alloy (i.e. pitting) is triggered prior to complete dissolution of the alumina film on the elsewhere still coated surface matrix.     

T–T–T behaviour of bioactive glasses 1–98 and 13–93

In this work crystallization kinetics of bioactive glasses 1–98 and 13–93 are discussed. Within a certain temperature–time window these glasses can be hot worked into various products without interfering with crystallization. The crystallization was studied isothermally by heating glass plates at different temperatures for different times. Phases in the samples were studied through XRD and SEM analyses. The nucleation-like curves and crystallization characteristics were measured with DTA. The temperature of maximum nucleation was measured for glass 1–98 at 725 °C and for 13–93 at 700 °C. The activation energy of crystallization of both glasses was 280 kJ/mol. The Johnson–Mehl–Avrami exponent and the SEM micrographs of the samples suggested surface crystallization. The primary crystalline phase was wollastonite. The growth rate of the crystallized surface layer was 1 order of magnitude higher in the plates of 1–98 than in 13–93. The results can be utilized to optimize the parameters in hot-working of the glasses.     

Bioavailability Studies and in vitro Profiling of the Selective Excitatory Amino Acid Transporter Subtype 1 (EAAT1) Inhibitor UCPH‐102

Although the selective excitatory amino acid transporter subtype 1 (EAAT1) inhibitor UCPH‐101 has become a standard pharmacological tool compound for in vitro and ex vivo studies in the EAAT research field, its inability to penetrate the blood–brain barrier makes it unsuitable for in vivo studies. In the present study, per os (p.o.) administration (40 mg kg^?1) of the closely related analogue UCPH‐102 in rats yielded respective plasma and brain concentrations of 10.5 and 6.67 μm after 1 h. Three analogue series were designed and synthesized to improve the bioavailability profile of UCPH‐102, but none displayed substantially improved properties in this respect. In vitro profiling of UCPH‐102 (10 μm ) at 51 central nervous system targets in radioligand binding assays strongly suggests that the compound is completely selective for EAAT1. Finally, in a rodent locomotor model, p.o. administration of UCPH‐102 (20 mg kg^?1) did not induce acute effects or any visible changes in behavior.