Pushing the speed limit in enantioselective supercritical fluid chromatography

Chromatographic enantioseparations on the order of a few seconds can be achieved by supercritical fluid chromatography using short columns packed with chiral stationary phases. The evolution of ‘world record’ speeds for the chromatographic separation of enantiomers has steadily dropped from an industry standard of 20–40 min just two decades ago, to a current ability to perform many enantioseparations in well under a minute. Improvements in instrument and column technologies enabled this revolution, but the ability to predict optimal separation time from an initial method development screening assay using the t_{min cc} predictor greatly simplifies the development and optimization of high‐speed chiral chromatographic separations. In this study, we illustrate how the use of this simple tool in combination with the workhorse technique of supercritical fluid chromatography on customized short chiral columns (1–2 cm length) allows us to achieve ultrafast enantioseparations of pharmaceutically relevant compounds on the 5–20 s scale, bringing the technique of high‐throughput enantiopurity analysis out of the specialist realm and into the laboratories of most researchers.     

Improved Thermal and Reusability Properties of Xylanase by Genipin Cross-Linking to Magnetic Chitosan Particles

Enzymes are gradually increasingly preferred over chemical processes, but commercial enzyme applications remain limited due to their low stability and low product recovery, so the application of an immobilization technique is required for repeated use. The aims of this work were to produce stable enzyme complexes of cross-linked xylanase on magnetic chitosan, to describe some characteristics of these complexes, and to evaluate the thermal stability of the immobilized enzyme and its reusability. A xylanase was cross-linked to magnetite particles prepared by in situ co-precipitation of iron salts in a chitosan template. The effect of temperature, pH, kinetic parameters, and reusability on free and immobilized xylanase was evaluated. Magnetization, morphology, size, structural change, and thermal behavior of immobilized enzyme were described. 1.0?±?0.1 μg of xylanase was immobilized per milligram of superparamagnetic chitosan nanoparticles via covalent bonds formed with genipin. Immobilized xylanase showed thermal, pH, and catalytic velocity improvement compared to the free enzyme and can be reused three times. Heterogeneous aggregates of 254 nm were obtained after enzyme immobilization. The immobilization protocol used in this work was successful in retaining enzyme thermal stability and could be important in using natural compounds such as Fe₃O₄@Chitosan@Xylanase in the harsh temperature condition of relevant industries.

     

Towards Controlled Graft Polymerization of Poly[styrene‐co‐(maleic anhydride)] on Functionalized Silica Mediated by Oxoaminium Bromide Salt. Facile Synthetic Pathway Using Nitroxide Chemistry

A TEMPO bromide salt is used to functionalize a silica surface with nitroxyl moieties. The functionalization reaction takes place in 48 h under mild conditions. In a second step, grafts of styrene‐maleic anhydride copolymer are grown from the functionalized silica surface by heating it in the presence of the monomers. FT‐IR and TGA analysis show that the silica was first functionalized with nitroxide moieties, and then that grafts of styrene‐maleic anhydride grew from the functionalized silica surface. A reaction mechanism is proposed in order to explain the findings. The results suggest that the oxoaminium salts are good candidates for the functionalization and grafting of surfaces that contain hydroxy groups and for the generation of hybrid materials with improved properties.

     

Chromatographic resolution of closely related species: Drug metabolites and analogs

In this study, we investigate the separation of a variety of mixtures of drugs, metabolites, and related analogs including representatives of the carbamazepine, methylated xanthine, steroid hormone, nicotine, and morphine families using several automated chromatographic method development screening systems including ultra high performance liquid chromatography, core–shell HPLC, achiral supercritical fluid chromatography (SFC), and chiral SFC. Of the 138 column and mobile phase combinations examined for each mixture, a few chromatographic conditions afford the best overall performance, with a single achiral SFC method (4.6 × 250 mm, 3.0 μm GreenSep Ethyl Pyridine, 25 mM isobutylamine in methanol/CO₂) affording good separation for all samples. Four of these mixtures were also resolved by achiral SFC on the Luna HILIC and chiral SFC Chiralpak IB columns using methanol or ethanol with 25 mM isobutylamine as polar modifiers. Modifications of standard chromatography screening conditions afforded fast separation methods (from 1 to 5 min) for baseline resolution of all components of each of these challenging sets of closely related compounds.     

Effect of the Addition of Alginate and/or Tetracycline on Brushite Cement Properties

Calcium phosphate cements have the advantage that they can be prepared as a paste that sets in a few minutes and can be easily adapted to the shape of the bone defect, which facilitates its clinical application. In this research, six formulations of brushite (dicalcium phosphate dihydrated) cement were obtained and the effect of the addition of sodium alginate was analyzed, such as its capacity as a tetracycline release system. The samples that contain sodium alginate set in 4 or 5 min and showed a high percentage of injectability (93%). The cements exhibit compression resistance values between 1.6 and 2.6 MPa. The drug was released in a range between 12.6 and 13.2% after 7 days. The antimicrobial activity of all the cements containing antibiotics was proven. All samples reached values of cell viability above 70 percent. We also observed that the addition of the sodium alginate and tetracycline improved the cell viability.     

Chemical composition and antioxidant activities of the essential oil from Tornabenea bischoffii (Apiaceae)

The chemical composition of Tornabenea bischoffii J. A. Schmidt essential oil from Cape Verde was studied by GC and GC/MS. Sixty volatile compounds were identified of which myristicin was the major constituent (33.6%). Using the 2,2-diphenyl-2-picrylhydrazyl free-radical scavenging method and the in vitro assay for prevention of lipid peroxidation by thiobarbituric reactive species, significant antioxidant activities were evidenced.     

Photoprotecting action and phytochemical analysis of a multiple radical scavenger lipophilic fraction obtained from the leaf of the seagrass Thalassia testudinum

The apolar fraction F1 of Thalassia testudinum was chemically characterized by gas chromatography-mass spectrometry, which led to the identification of 43 metabolites, all of them reported for the first time in the genus Thalassia. More than 80% of the F1 composition was constituted by aromatic metabolites including the major components 1,1-bis(p-tolyl)ethane (6.0%), 4,4'-diisopropylbiphenyl (4.8%) and a 1,1-bis(p-tolyl)ethane isomer (4.7%). This lipophilic fraction was assayed for its antioxidant effects and skin protective action. In vitro assays showed that F1 strongly scavenged DPPH* (IC(50) 312.0 ± 8.0 μg mL(-1)), hydroxyl (IC(50) 23.8 ± 0.5 μg mL(-1)) and peroxyl radical (IC(50) 6.6 ± 0.3 μg mL(-1) ), as well as superoxide anion (IC(50) 50.0 ± 0.7 μg mL(-1)). Also, F1 markedly inhibited the spontaneous lipid peroxidation (LPO) in brain homogenates (IC(50) 93.0 ± 6.0 μg mL(-1)) and the LPS-stimulated nitrite generation on RAW624.7 macrophages (58.6 ± 3.2%, 400 μg mL(-1)). In agreement with these findings, its topical application at 250 and 500 μg cm(-2) strikingly reduced skin damage on mice exposed to acute UVB radiation by 45% and 70%, respectively and significantly attenuated the LPO developed following the first 48 h after acute exposure to UVB irradiation, as manifested by the decreased malondialdehide level and by the increased of reduced gluthatione content. Our results suggest that F1 may contribute to skin repair by attenuating oxidative stress due to its antioxidant activity.