Repurposing the Pummerer Rearrangement: Determination of Methionine Sulfoxides in Peptides

The reversible oxidation of methionine residues in proteins has emerged as a biologically important post-translational modification. However, detection and quantitation of methionine sulfoxide in proteins is difficult. Our aim is to develop a method for specifically derivatizing methionine sulfoxide residues. We report a Pummerer rearrangement of methionine sulfoxide treated sequentially with trimethylsilyl chloride and then 2-mercaptoimidazole or pyridine-2-thiol to produce a dithioacetal product. This derivative is stable to standard mass spectrometry conditions, and its formation identified oxidized methionine residues. The scope and requirements of dithioacetal formation are reported for methionine sulfoxide and model substrates. The reaction intermediates have been investigated by computational techniques and by ¹³C NMR spectroscopy. These provide evidence for an α-chlorinated intermediate. The derivatization allows for detection and quantitation of methionine sulfoxide in proteins by mass spectrometry and potentially by immunochemical methods.     

Intergroup relations and group solidarity: Effects of group identification and social beliefs on depersonalized attraction.

An intergroup extension of M. A. Hogg's (1992, 1993) social attraction hypothesis is proposed. Netball teams were investigated with measures assessing the relationship between (a) objective status; (b) "social beliefs" about intergroup status, stability, legitimacy, and permeability; (c) group identification, self-categorization, and prototypicality; (d) interpersonal relations and similarity; (e) depersonalized social attraction; and (f) true personal attraction. As predicted, group-membership based social attraction was directly influenced by self-categorization; indirectly influenced, through self-categorization, by intergroup status and stability beliefs; and uninfluenced by interpersonal relations. Social attraction (related to prototypicality and group identification) was relatively independent of personal attraction (related to similarity and interpersonal variables). Legitimacy, permeability, and the empirical co-occurrence of social and personal attraction in cohesive groups are discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Liquefaction of coal using supercritical fluid mixtures

Powhatan No. 5 and Bruceton coals were liquefied for 15–60 min at 653 K and 30 MPa in supercritical aqueous mixtures containing 10–20 wt% tetrahydroquinoline (THQ), quinoline or tetralin. The THQ-water mixtures produced the highest conversion to tetrahydrofuran (THF) soluble products (up to 74%). Tetralin-water, quinoline-water and pure water solvents gave increasingly lower yields of THF solubles. Addition of hydrogen to the quinoline-water solvent mixture increased yields slightly, but not to the level obtained using the THQ-water mixture.The yields of THF solubles in all instances depended upon the concentration of solvent in the mixture, with the 10 wt% THQ and 10 wt% tetralin (in water) giving higher yields than either 0 or 20 wt% concentrations. The nitrogen-containing solvents were chemically bonded to the THF-soluble product, as observed by g.p.c.     

Flow patterns in granulating systems

Particle flow patterns were investigated for wet granulation and dry powder mixing in ploughshare mixers using Positron Emission Particle Tracking (PEPT). In a 4-l mixer, calcium carbonate with mean size 45 μm was granulated using a 50 wt.% solution of glycerol and water as binding fluid, and particle movement was followed using a 600-μm calcium hydroxy-phosphate tracer particle. In a 20-l mixer, dry powder flow was studied using a 600-μm resin bead tracer particle to simulate the bulk polypropylene powder with mean size 600 μm. Important differences were seen between particle flow patterns for wet and dry systems. Particle speed relative to blade speed was lower in the wet system than in the dry system, with the ratios of average particle speed to blade tip speed for all experiments in the range 0.01–0.25. In the axial plane, the same particle motion was observed around each blade; this provides a significant advance for modelling flow in ploughshare mixers. For the future, a detailed understanding of the local velocity, acceleration and density variations around a plough blade will reveal the effects of flow patterns in granulating systems on the resultant distribution of granular product attributes such as size, density and strength.     

The Application of Mealworm (Tenebrio molitor) Oil in Cosmetic Formulations

The depletion of natural resources, the increasing use of valuable land surface for human activities, and the generation of waste are detrimental to the planet. Sustainable alternatives to guarantee a sufficient supply of food, feed, and biomaterials are needed. Insects may hold an interesting position in a circular economy to tackle contemporary societal challenges. Using insects for food, feed, biomaterial production, and to valorize side-streams, have gained increased interest. Mealworms are amenable to large-scale farming. Herein, the potential of mealworm oil for implementation in a cosmetic hand cream is evaluated. It is shown that mealworms are rich in oil (≈30% of the dry weight), and the oil can be extracted using hexane or ethyl acetate as a solvent. The euthanization step of mealworms has profound effect on the free fatty acid content. The fatty acid profile indicates a large proportion of unsaturated fatty acids, which is promising for use in cosmetic applications. In a proof of concept, the mealworm oil is implemented in a hand cream and compared to hand cream containing macadamia nut oil. No differences in odor and aspect/stability are observed, but mealworm creams are slightly less white color. Mealworm oil is suitable for cosmetics applications. Practical applications: Several insect species can be sustainably reared on low-value organic side-streams, requiring only small amounts of land-surface, less water, and producing less greenhouse gases. In addition, they have short life cycles and can be reared continuously and locally. This implies that insects are an interesting source of biological materials including proteins and oils. Insect oils, including oil of mealworms, have interesting fatty acid profiles that make them amenable to replace oils of vegetable origin for applications within cosmetics. The results indicate that mealworm oil can be a novel, sustainable ingredient for use in the cosmetics industry.     

Degradation and Mechanical Behavior of Fish Gelatin/Polycaprolactone AC Electrospun Nanofibrous Meshes

With the increasing interest in biopolymer nanofibers for diverse applications, the characterization of these materials in the physiological environment has become of equal interest and importance. This study performs first-time simulated body fluid (SBF) degradation and tensile mechanical analyses of blended fish gelatin (FGEL) and polycaprolactone (PCL) nanofibrous meshes prepared by a high-throughput free-surface alternating field electrospinning. The thermally crosslinked FGEL/PCL nanofibrous materials with 84–96% porosity and up to 60 wt% PCL fraction demonstrate mass retention up to 88.4% after 14 days in SBF. The trends in the PCL crystallinity and FGEL secondary structure modification during the SBF degradation are analyzed by Fourier transform infrared spectroscopy. Tensile tests of such porous, 0.1–2.2 mm thick FGEL/PCL nanofibrous meshes in SBF reveal the ultimate tensile strength, Young's modulus, and elongation at break within the ranges of 60–105 kPa, 0.3–1.6 MPa, and 20–70%, respectively, depending on the FGEL/PCL mass ratio. The results demonstrate that FGEL/PCL nanofibrous materials prepared from poorly miscible FGEL and PCL can be suitable for selected biomedical applications such as scaffolds for skin, cranial cruciate ligament, articular cartilage, or vascular tissue repair.     

Interlaboratory study on lipid oxidation during accelerated storage trials with rapeseed and sunflower oil analyzed by conjugated dienes as primary oxidation products

Accelerated storage tests are frequently used to assess the oxidative stability of foods and related systems due to its reproducibility. Various methods and experimental conditions are used to measure lipid oxidation. Differences between laboratories make it necessary to determine the repeatability and reproducibility of oxidation tests performed under the same conditions. The objective of the present interlaboratory study was to evaluate the outcome of a storage test for two different bulk oils, sunflower oil (SFO) and rapeseed oil (RSO), during a period of 9 weeks at 20°C, 30°C, 40°C, and 60°C. Sixteen laboratories were provided with bottled oils and conducted the storage tests according to a detailed protocol. Lipid oxidation was monitored by the formation of conjugated dienes (CD) and the activation energy (E_a) was determined for comparative purposes and statistically evaluated. An increase in CD formation was observed for both oils when the storage temperature was increased in all laboratories. The E_a,1 ranged from 47.9 to 73.3 kJ mol⁻¹ in RSO and from 27.8 to 62.6 kJ mol⁻¹ in SFO, with average values of 58.2 and 46.8 kJ mol⁻¹, respectively. The reproducibility coefficients were 10.9% and 18.2% for RSO and SFO, respectively. Practical applications: In order to compare results on oxidative stability of foods derived from different studies, the reproducibility of storage tests and methods employed to evaluate the oxidation level should be considered. This study provides fundamental data on the reproducibility of lipid oxidation under accelerated storage conditions and defines important parameters to be considered for the conduction of experiments.     

Imaging of KCa3.1 Channels in Tumor Cells with PET and Small-Molecule Fluorescent Probes

The Ca²⁺ activated K⁺ channel K_Ca3.1 is overexpressed in several human tumor cell lines, e. g. clear cell renal carcinoma, prostate cancer, non-small cell lung cancer. Highly aggressive cancer cells use this ion channel for key processes of the metastatic cascade such as migration, extravasation and invasion. Therefore, small molecules, which are able to image this K_Ca3.1 channel in vitro and in vivo represent valuable diagnostic and prognostic tool compounds. The [¹⁸F]fluoroethyltriazolyl substituted senicapoc was used as positron emission tomography (PET) tracer and showed promising properties for imaging of K_Ca3.1 channels in lung adenocarcinoma cells in mice. The novel senicapoc BODIPY conjugates with two F-atoms ( 9 a ) and with a F-atom and a methoxy moiety ( 9 b ) at the B-atom led to the characteristic punctate staining pattern resulting from labeling of single K_Ca3.1 channels in A549-3R cells. This punctate pattern was completely removed by preincubation with an excess of senicapoc confirming the high specificity of K_Ca3.1 labeling. Due to the methoxy moiety at the B-atom and the additional oxyethylene unit in the spacer, 9 b exhibits higher polarity, which improves solubility and handling without reduction of fluorescence quantum yield. Docking studies using a cryo-electron microscopy (EM) structure of the K_Ca3.1 channel confirmed the interaction of 9 a and 9 b with a binding pocket in the channel pore.     

The effectuation of seawater on the microstructural features and the compressive strength of fly ash blended cement at early and later ages

The current work scrutinizes the effectuation of seawater on morphological properties, pore structure, and compressive strength during the hydration process of fly ash blended cement at 3, 7, 28, 56, and 90 days to better understand the influence of salinity conditions of seawater on the microstructural modification and strength development of the hydration products as well as the total porosity. The chemical reaction's mechanism of mightily soluble salts, for example, Mg₂SO₄ and NaCl, with hydrated fly ash and blended cement (calcium-bearing phases) was also confirmed. Fourier-transform infrared spectroscopy has been appointed to observe and characterize the energetics of variation in the formulation of portlandite (CH), calcium silicate hydrate, gypsum (Gy), ettringite (AFt), and calcium chloroaluminate (Friedel's salt [FS]) throughout the hydration process of fly ash blended cement with seawater in comparison with deionized water. X-ray diffraction analysis exposed that the peak intensities of FS, portlandite, and some particular phases of the hydrated fly ash blended cement in seawater are higher and sharper than the comparable peaks in deionized water. Mercury intrusion porosimetry-measurements have been appointed that the total porosity of artificial seawater (ASW) was decreased from 28.9% at 3 days to 19.4% at 56 days. In addition, the average, median, and critical pore diameter were decreased in ASW while compared to deionized water (DIW). The reaction products of this work were also characterized using scanning electron microscopy, EDS, compressive strength, and isothermal calorimeter.