Simultaneous Determination of Alpha-Tocopherol and Alpha-Tocopheryl Acetate in Dairy Products,Plant Milks and Health Supplements by Using SPE and HPLC Method

A solid phase extraction technique for sample cleanup and extraction of α-tocopherol and α-tocopheryl acetate is described and applied to their simultaneous HPLC analysis in dairy products, plant-based milks, infant formulas, and pharmaceutical colostrum. The proposed method includes sample pretreatment by using ethanol, followed by solid-phase extraction of the organic supernatant on C18 cartridges. The identification and quantification were done by reversed-phase HPLC with fluorescence detection (ex 295 nm, em 330 nm) for tocopherol and with UV detector set at 220 nm for tocopheryl acetate. The mobile phase consisted of 100% acetonitrile. The linear ranges were from 0.02–0.40 μg/mL (dairy products) and 0.50–5.00 μg/mL (plant milks, infant formulas, powdered products) for α-tocopherol and those of α-tocopheryl acetate were from 0.20–2.00 μg/mL (dairy products) and 1.00–10.0 μg/mL (plant milks, infant formulas, powdered products). The LOD and LOQ of α-tocopherol were 0.1 and 0.4 μg/mL, while those of the α-tocopheryl acetate were 2.0 μg/mL for LOD and 6.0 μg/mL for LOQ. The method gave extraction recoveries from 73–94% with RSDs values being 5–10%. This method is simple, SPE procedure is fast and HPLC analysis time is less than 10 min. The total time of performing analysis per sample is less than 1 h. The important advantage of the proposed method is the capability of determining and reporting α-tocopherol and α-tocopheryl acetate separately. Moreover, the developed method is suitable for fast screening of the synthetic form of vitamin E in dairy products, plant-based milks, infant formulas, and pharmaceutical colostrum.     

Introducing Enantioselective Ultrahigh-Pressure Liquid Chromatography (eUHPLC): Theoretical Inspections and Ultrafast Separations on a New Sub-2-μm Whelk-O1 Stationary Phase

A new chiral stationary phase for ultrahigh-pressure liquid chromatography (UHPLC) applications was prepared by covalent attachment of the Whelk-O1 selector to spherical, high-surface-area 1.7-μm porous silica particles. Columns of varying dimensions (lengths of 50, 75, 100, and 150 mm and internal diameters of 3.0 or 4.6 mm) were packed and characterized in terms of permeability, efficiency, retention, and enantioselectivity, using both organic and water-rich mobile phases. A conventional HPLC Whelk-O1 column based on 5.0-μm porous silica particles and packed in a 250 mm × 4.6 mm column was used as a reference. Van Deemter curves, generated with low-molecular-weight solutes on a 100 mm × 4.6 mm column packed with the 1.7-μm particles, showed H(min) (μm) and μ(opt) (mm/s) values of 4.10 and 5.22 under normal-phase and 3.74 and 4.34 under reversed-phase elution conditions. The flat C term of the van Deemter curves observed with the 1.7-μm particles allowed the use of higher-than-optimal flow rates without significant efficiency loss. Kinetic plots constructed from van Deemter data confirmed the ability of the column packed with the 1.7-μm particles to afford subminute separations with good efficiency and its superior performances in the high-speed regime, compared to the column packed with 5.0-μm particles. Resolutions in the time scale of seconds were obtained using a 50-mm-long column in the normal phase or polar organic mode. The intrinsic kinetic performances of 1.7-μm silica particles are retained in the Whelk-O1 chiral stationary phase, clearly demonstrating the potentials of enantioselective UHPLC in terms of high speed, throughput, and resolution.     

Characterization of B4C-SiC ceramic composites prepared by ultra-high pressure sintering

Additive-free boron carbide (B₄C) – silicon carbide (SiC) ceramic composites with different B₄C and β-SiC powders ratio were densified using the high-pressure “anvil-type with hollows” apparatus at 1500 °C under a pressure of 4 GPa for 60 s in air. The effect of starting powders ratio on the composites sintering behavior, relative density, microstructural development, and thermomechanical properties was studied. The sintered samples hardness was found to be in the range from 24 to 31 GPa. The thermal conductivity measurements, conducted in the temperature range from room temperature to 1000 °C, showed that the thermal diffusivity of sintered samples was between 6 and 9.5 mm²/s whereas the thermal conductivity was in the range from 16 to 28 W/(m K). The results of this study show that the high-pressure sintering can be a very effective low-temperature densification method for the obtainment of additive-free B₄C - β-SiC ceramic composites.     

Structure,electrochemical impedance and Raman spectroscopy of lithium-niobium-titanium-oxide ceramics for LTCC technology

Resultsof Electrochemical Impedance Spectroscopy (EIS) are reported for lithium-niobium-titanium-oxide (LNTO) ceramics synthesized by a solid-state reaction method with two functional additives (MoO₃ or ZnO) in the temperature range 323 K - 573 K and frequencies between 10^?1 Hz and 10⁷ Hz. Scanning electron microscopy (SEM) reveals a textured morphology of rod and plate-like particles that are typical for M-phase LNTO materials, while X-ray diffraction (XRD) analysis confirms the formation of an M-phase member compound with an approximate structure of Li₇Nb₃Ti₅O₂₁. Complex impedance analysis indicates that its overall electrical resistivity behavior depends mostly on the grain boundary processes. EIS analysis shows a negative temperature coefficient of resistance behavior (NTCR) in a defined temperature range in two LNTOs and thermal activation of the conduction mechanisms. The low dielectric constants of 5.5 and 12.1 at 1 MHz were found for the first and second LNTOs, respectively. Complimentary Raman spectroscopic measurements, despite very large crystallographic unit cell of LNTO, reveal only a small number of lines, which is the consequence of a “molecular” nature of materials.     

Front Cover: Structure-Based Design,Synthesis, and Biological Evaluation of Triazole-Based smHDAC8 Inhibitors (ChemMedChem 7/2020)

Schistosomiasis is a neglected tropical disease caused by parasitic flatworms of the genus Schistosoma, which affects over 200 million people worldwide and leads to at least 300,000 deaths every year. In this study, initial screening revealed the triazole-based hydroxamate 2 b (N-hydroxy-1-phenyl-1H-1,2,3-triazole-4-carboxamide) exhibiting potent inhibitory activity toward the novel antiparasitic target Schistosoma mansoni histone deacetylase 8 (smHDAC8) and promising selectivity over the major human HDACs. Subsequent crystallographic studies of the 2 b /smHDAC8 complex revealed key interactions between the inhibitor and the enzyme's active site, thus explaining the unique selectivity profile of the inhibitor. Further chemical modifications of 2 b led to the discovery of 4-fluorophenoxy derivative 21 (1-[5-chloro-2-(4-fluorophenoxy)phenyl]-N-hydroxy-1H-1,2,3-triazole-4-carboxamide), a nanomolar smHDAC8 inhibitor (IC₅₀=0.5 μM), exceeding the smHDAC8 inhibitory activity of 2 b and SAHA (vorinostat), while exhibiting an improved selectivity profile over the investigated human HDACs. Collectively, this study reveals specific interactions between smHDAC8 and the synthesized triazole-based inhibitors and demonstrates that these small molecules represent promising lead structures, which could be further developed in the search for novel drugs for the treatment of schistosomiasis.     

An Evaluation of Steel Embrittlement Caused by Welding

The fracture toughness of the HAZ in welds on a HSLA structural steel was assessed by using two types of precracked small-scale fracture-mechanics specimens. The microstructure of the single- and double-pass HAZs was simulated on a Gleeble machine at two different cooling rates. A direct measurement of K_Ic was not possible due to the limited size of both kinds of specimens. A suitable adaptation of the loading diagrams was performed in order to produce relevant data about the fracture properties of the investigated sub-zones of the HAZ.     

Liquid–liquid equilibrium for the systems hydrocarbon–thiophene or pyridine–1-hexyl-3,5-dimethylpyridinium bis(trifluoromethylsulfonyl)imide

Liquid–liquid equilibrium for eight ternary systems involving one hydrocarbon (n-hexane, n-heptane, i-octane or toluene), thiophene or pyridine and an ionic liquid (1-hexyl-3,5-dimethylpyridinium bis(trifluoromethylsulfonyl)imide) was experimentally determined at atmospheric pressure and 25°C. Equilibrium data are presented with binodal curves as well as with tie lines. The suitability of ionic liquid (IL) for extractive desulfurization and denitrification was evaluated in terms of solute distribution ratio and selectivity. Extraction experiments with three-component and seven-component (n-hexane, n-heptane, i-octane, toluene, thiophene, pyridine and IL) systems have been performed. The equilibrium data in three-component systems were well described with Non-Random Two-Liquid (NRTL) and Universal Quasi-Chemical (UNIQUAC) models.     

DMSO Chemically Alters Cell Membranes to Slow Exocytosis and Increase the Fraction of Partial Transmitter Released

Dimethyl sulfoxide (DMSO) is frequently used as a solvent in biological studies and as a vehicle for drug therapy; but the side effects of DMSO, especially on the cell environment, are not well understood, and controls with DMSO are not neutral at higher concentrations. Herein, electrochemical measurement techniques are applied to show that DMSO increases exocytotic neurotransmitter release, while leaving vesicular contents unchanged. In addition, the kinetics of release from DMSO‐treated cells are faster than that of untreated ones. The results suggest that DMSO has a significant influence on the chemistry of the cell membrane, leading to alteration of exocytosis. A speculative chemical mechanism of the effect on the fusion pore during exocytosis is presented.     

PM6 and DFT study of free radical scavenging activity of morin

Flavonoids have long been recognised for their general health-promoting properties, of which their antioxidant activity may play an important role. In this work, we have studied the properties of flavonoid morin using semiempirical and density functional theory (DFT) methods in order to validate the application of the recently developed parametric method 6 (PM6). Reaction enthalpies related to mechanisms of free radical scavenging by flavonoid morin were calculated by DFT and PM6 methods in gas-phase, water, DMSO and benzene. It has been shown that fast semiempirical PM6 method can mimic results obtained by means of more accurate time consuming DFT calculations. Thermodynamically favoured mechanism depends on reaction medium: SPLET (sequential proton loss electron transfer) is preferred in water and DMSO, and HAT (hydrogen atom transfer) is predominant in gas-phase. In benzene these two mechanisms are competitive.