π‐Expanded α,β‐Unsaturated Ketones: Synthesis,Optical Properties,and Two‐Photon‐Induced Polymerization

A library of π‐expanded α,β‐unsaturated ketones was designed and synthesized. They were prepared by a combination of Wittig reaction, Sonogashira reaction, and aldol condensation. It was further demonstrated that the double aldol condensation can be performed effectively for highly polarized styrene‐ and diphenylacetylene‐derived aldehydes. The strategic placement of two dialkylamino groups at the periphery of D ‐π‐A‐π‐D molecules resulted in dyes with excellent solubility. These ketones absorb light in the region 400–550 nm. Many of them display strong solvatochromism so that the emission ranges from 530–580 nm in toluene to the near‐IR region in benzonitrile. Ketones based on cyclobutanone as central moieties display very high fluorescence quantum yields in nonpolar solvents, which decrease drastically in polar media. Photophysical studies of these new functional dyes revealed that they possess an enhanced two‐photon absorption cross section when compared with simpler ketone derivatives. Due to strong polarization of the resulting dyes, values of two‐photon absorption cross sections on the level of 200–300 GM at 800 nm were achieved, and thanks to that as well as the presence of the keto group, these new two‐photon initiators display excellent performance so that the operating region is 5–75 mW in some cases.     

In-bone protein digestion followed by LC-MS/MS peptide analysis as a new way towards the routine proteomic characterization of human maxillary and mandibular bone tissue in oral surgery

Proteomic characterization of alveolar bones in oral surgery represents an analytical challenge due to their insoluble character. The implementation of a straightforward technique could lead to the routine use of proteomics in this field. This work thus developed a simple technique for the characterization of bone tissue for human maxillary and mandibular bones. It is based on the direct in-bone tryptic digestion of proteins in both healthy and pathological human maxillary and mandibular bone samples. The released peptides were then identified by the LC-MS/MS. Using this approach, a total of 1120 proteins were identified in the maxillary bone and 1151 proteins in the mandibular bone. The subsequent partial least squares–discrimination analysis (PLS-DA) of protein data made it possible to reach 100% discrimination between the samples of healthy alveolar bones and those of the bone tissue surrounding the inflammatory focus. These results indicate that the in-bone protein digestion followed by the LC-MS/MS and subsequent statistical analysis can provide a deeper insight into the field of oral surgery at the molecular level. Furthermore, it could also have a diagnostic potential in the differentiation between the proteomic patterns of healthy and pathological alveolar bone tissue. Data are available via ProteomeXchange with the identifier PXD026775.     

Influence of Extraction Solvent on the Phenolic Profile and Bioactivity of Two Achillea Species

The phenolic composition, as well as the antioxidant and antimicrobial activities of two poorly investigated Achillea species, Achillea lingulata Waldst. and the endemic Achillea abrotanoides Vis., were studied. To obtain a more detailed phytochemical profile, four solvents with different polarities were used for the preparation of the plant extracts whose phenolic composition was analyzed using UHPLC-MS/MS (ultra-high performance liquid chromatography-tandem mass spectrometry). The results indicate that both of the investigated Achillea species are very rich in both phenolic acids and flavonoids, but that their profiles differ significantly. Chloroform extracts from both species had the highest yields and were the most chemically versatile. The majority of the examined extracts showed antimicrobial activity, while ethanolic extracts from both species were potent against all tested microorganisms. Furthermore, the antioxidant activity of the extracts was evaluated. It was found that the ethanolic extracts possessed the strongest antioxidant activities, although these extracts did not contain the highest amounts of detected phenolic compounds. In addition, several representatives of phenolic compounds were also assayed for these biological activities. Results suggest that ethanol is a sufficient solvent for the isolation of biologically active compounds from both Achillea species. Moreover, it was shown that the flavonoids naringenin and morin are mainly responsible for these antimicrobial activities, while caffeic, salicylic, chlorogenic, p-coumaric, p-hydroxybenzoic, and rosmarinic acid are responsible for the antioxidant activities of the Achillea extracts.     

Pore-Scale Analysis of NAPL Blob Dissolution and Mobilization in Porous Media

A pore-scale analysis of nonaqueous phase liquid (NAPL) blob dissolution and mobilization in porous media was presented. Dissolution kinetics of residual NAPLs in an otherwise water-saturated porous medium was investigated by conducting micromodel experiments. Changes in residual NAPL volume were measured from recorded video images to calculate the mass transfer coefficient, K and the lumped mass transfer rate coefficient, k. The morphological characteristics of the blobs such as specific and intrinsic area were found to be independent of water flow rate except at NAPL saturations below 2%. Dissolution process was also investigated by separating the mass transfer into zones of mobile and immobile water. The fractions of total residual NAPL perimeters in contact with mobile water and immobile water were measured and their relationship to the mass transfer coefficient was discussed. In general, residual NAPLs are removed by dissolution and mobilization. Although these two mechanisms were studied individually by others, their simultaneous occurrence was not considered. Therefore, in this study, mobilization of dissolving NAPL blobs was investigated by an analysis of the forces acting on a trapped NAPL blob. A dimensional analysis was performed to quantify the residual blob mobilization in terms of dimensionless Capillary number (Ca _I). If Ca _I is equal to or greater than the trapping number defined as , then blob mobilization is expected.     

Evaluation of calcium carbonate in eggshells using thermal analysis

The eggshell of the hen is an important structure which provides protection for the developing chick, and also a container for the egg in the food industry. Egg breakage can reach up to 10% of total egg production, causing considerable economic losses. The eggshell consists of membranes, composed mainly of proteins, and the mineral shell composed mainly of the calcite polymorph of CaCO₃. The average CaCO₃ content of a chicken eggshell is between 93 and 97%, depending on animal genotype, age, housing system of laying hens and mineral nutrition. In the present study, eggs of the same breed and approximately same age were collected from four different production systems: organic farming, free-range production, deep litter system and battery cage system. The CaCO₃ content was determined by the standard titration method and by atomic absorption spectroscopy. Thermal properties of dried eggshell powder were measured by thermogravimetric measurements between 30 and 900 °C in air, showing a significant mass loss of?≈?43% between 600 and 850 °C corresponding to the decomposition of CaCO₃ to CaO and CO₂. The relations between the thermal mass loss and CaCO₃ content determined by the titration method/atomic absorption spectroscopy were studied using predictive models fitted by the linear regression method. A good prediction ability with an average prediction error of 0.01% was obtained between CaCO₃ determined by titration and the thermal mass loss, indicating that TG could provide a reliable method for evaluation of CaCO₃ content in eggshells.

     

A simple method to prepare high surface area activated carbon from carboxyl methyl cellulose by low temperature physical activation

Activated carbon with high surface area was prepared from sodium salt of carboxyl methyl cellulose by physical activation at 400 °C followed by treatment in boiling water. The carbon was characterized by XRD, SEM, EPR, TG, IR, surface areas and porosity measurements. The carbon showed alkaline reaction in aqueous solution. It showed high surface area and pore volume in comparison to two commercially available carbons.     

Metabolism of JWH-015, JWH-098, JWH-251, and JWH-307 in silico and in vitro: a pilot study for the detection of unknown synthetic cannabinoids metabolites

This pilot study was performed to study the main metabolic reactions of four synthetic cannabinoids: JWH-015, JWH-098, JWH-251, and JWH-307 in order to setup a screening method for the detection of main metabolites in biological fluids. In silico prediction of main metabolic reactions was performed using MetaSite^? software. To evaluate the agreement between software prediction and experimental reactions, we performed in vitro experiments on the same JWHs using rat liver slices. The obtained samples were analyzed by liquid chromatography-quadrupole time-of-flight and the identification of metabolites was executed using Mass-MetaSite^? software that automatically assigned the metabolite structures to the peaks detected based on their accurate masses and fragmentation. A comparison between the experimental findings and the in silico metabolism prediction using MetaSite^? software showed a good accordance between experimental and in silico data. Thus, the use of in silico metabolism prediction might represent a useful tool for the forensic and clinical toxicologist to identify possible main biomarkers for synthetic cannabinoids in biological fluids, especially urine, following their administration.

Effects of interface contacts on the magneto electro-elastic coupling for fiber reinforced composites

Imperfect bonding between constituents is studied where displacements, electric and magnetic static potentials are considered to have a jump proportional to the normal component of the mechanical traction, electric displacement and magnetic flux. This condition may model various interface damages or the thin glue layer between two adjacent phases. They are termed as the mechanically compliant, dielectrically weakly capacitance and magnetically weakly inductance at the interface. It is shown that while the more imperfect the interface is, the overall properties become weaker, such as longitudinal shear stiffness, out-of-plane piezoelectric coupling, and magnetoelectric coupling. Out-of-plane piezomagnetic coupling, transverse dielectric permittivity and transverse dielectric permeability exhibit no influence by imperfect bonding. The imperfect interface proposed is mimicked by the springs, capacitors and inductances for the mechanical, electric and magnetic interaction between the phases and are highly sensitive to the interphase properties. The results are compared mainly with the self consistent model reported in the literature and good agreements are shown.     

Application of ultrasound‐assisted liquid–liquid microextraction coupled with gas chromatography and mass spectrometry for the rapid determination of synthetic cannabinoids and metabolites in biological samples

The constant emergence of new psychoactive substances is a challenge to clinical and forensic toxicologists who need to constantly update analytical techniques to detect them. A large portion of these substances are synthetic cannabinoids. The aim of this study was to develop a rapid and simple method for the determination of synthetic cannabinoids and their metabolites in urine and blood using gas chromatography–mass spectrometry. The method involves an ultrasound‐assisted dispersive liquid–liquid microextraction that implies a rapid procedure, giving excellent extraction efficiencies with minimal use of toxic solvents. This is followed by silylation and analysis with gas chromatography–mass spectrometry. The chromatographic method allows for the separation and identification of 29 selected synthetic cannabinoids and some metabolites. The method was validated on urine and blood samples with the ability to detect and quantify all analytes with satisfactory limits of detection (from 1 to 5 ng/mL), limits of quantification (5 ng/mL), and selectivity and linearity (in the range of 5–200 ng/mL). The developed assay is highly applicable to laboratories with limited instrumental availability, due to the use of efficient and low‐cost sample preparation and instrumental equipment. The latter may contribute to enhance the detection of new psychoactive substances in clinical and forensic toxicology laboratories.