The Oxidation of Thiols by Flavoprotein Oxidases: a Biocatalytic Route to Reactive Thiocarbonyls

Flavoprotein oxidases are a diverse class of biocatalysts, most of which catalyze the oxidation of C? O, C? N, or C? C bonds. Flavoprotein oxidases that are known to catalyze the oxidation of C? S bonds are rare, being limited to enzymes that catalyze the oxidative cleavage of thioethers. Herein, we report that various flavoprotein oxidases, previously thought to solely act on alcohols, also catalyze the oxidation of thiols to thiocarbonyls. These results highlight the versatility of enzymatic catalysis and provide a potential biocatalytic route to reactive thiocarbonyl compounds, which have a variety of applications in synthetic organic chemistry.     

Some trends in the theory of groups with finitely many normalizers

Ricerche di Matematica - This paper provides an account of results and methods from the theory of infinite groups admitting only finitely many normalizers of subgroups with a given property. Some...     

Certification of nitrate in spinach powder reference material SPIN-1 by high-precision isotope dilution GC–MS

A high-precision exact-matching quadruple isotope dilution method (ID⁴MS) was employed for the quantitation of nitrate in an air-dried spinach powder Certified Reference Material (CRM). The analyte was extracted in hot water following addition of ¹⁵NO\({}_{3}^{-}\) internal standard. The blend was then treated with sulfamic acid to remove nitrite and with triethyloxonium tetrafluoroborate to promote aqueous conversion of nitrate into volatile EtONO₂. The derivative was analyzed by headspace GC–MS with 3-min elution time. The method performance was validated with a series of tests which demonstrated adequate selectivity and ruggedness. This method supported the development of novel SPIN-1 CRM giving a modest contribution to its uncertainty (u_char = 0.85%). With respect to previous attempts, the SPIN-1 was proven stable, homogeneous (u_hom = 0.44%), and suitable for spinach monitoring under EU regulations. On dried basis, the nitrate content of SPIN-1 was found to be 22.53 ± 0.43 mg/g (U_c = 1.9%, k = 2). The material was also used in an inter-laboratory study where four laboratories employed a total of ten measurement methods.

SPIN-1 Certified Reference Material for nitrate in spinach powder

     

Emergent biaxiality in nematic microflows illuminated by a laser beam

Anisotropic fluids (e.g. liquid crystals) offer a remarkable promise as optofluidic materials owing to the directional, tunable, and coupled interactions between the material, flow, and the optical fields. Here we present a comprehensive in silico treatment of this anisotropic interaction by performing nonequilibrium molecular dynamics simulations. We quantify the response of a nematic liquid crystal (NLC) undergoing a Poiseuille flow in the Stokes regime, while being illuminated by a laser beam incident perpendicular to the flow direction. We adopt a minimalistic model to capture the interactions, accounting for two features: first, the laser heats up the NLC locally; and second, the laser polarises the NLC and exerts an optical torque that tends to reorient molecules of the nematic phase. Because of this reorientation the liquid crystal exhibits small regions of biaxiality, where the nematic director is one symmetry axis and the axis of rotation for the reorientation of the molecules is the other one. We find that the relative strength of the viscous and the optical torques mediates the flow-induced response of the biaxial regions, thereby tuning the emergence, shape and location of the regions of enhanced biaxiality. The mechanistic framework presented here promises experimentally tractable routes toward novel optofluidic applications based on material-flow-light interactions.     

Determination of fexofenadine in Hank's balanced salt solution by high‐performance liquid chromatography with ultraviolet detection: application to Caco‐2 cell permeability studies

The drug‐transporting proteins can affect the pharmacokinetics and pharmacodymanics of many drugs, resulting in an erratic and unpredictable pharmacological response. The Caco‐2 monolayer is routinely applied to investigate the carrier‐mediated transport of drugs. Therefore, the selection of a marker compound able to characterize the activity of such transporters is crucial. Fexofenadine (FEX), a P‐gp/OATP substrate, can be considered a suitable probe. However, in order to use be used as a marker compound, it is mandatory to develop an analytical method able to quantify this drug during the in vitro permeability assay. An HPLC method with ultraviolet detection was developed; the mobile phase consisted of phosphate buffer (pH 3.2) containing 10 m m of sodium octanosulphonate and acetonitrile (60:40) and the flow rate was set at 1.2 mL/min. Fexofenadine was eluted at 40°C, the retention time was about 4.6 min. The LOD and LOQ values were 1.9 and 6.2 ng/mL, respectively. Verapamil and ketoconazole, the most common P‐gp inhibitors, were eluted as distinct peaks of that corresponding to fexofenadine The method was successfully applied to quantify the amount of FEX transported across the Caco‐2 monolayer and could be an additional tool for those investigating the role of membrane transporters on drug absorption. Copyright © 2014 John Wiley & Sons, Ltd.     

Continuous‐Flow Microwave Synthesis of Metal–Organic Frameworks: A Highly Efficient Method for Large‐Scale Production

Metal–organic frameworks are having a tremendous impact on novel strategic applications, with prospective employment in industrially relevant processes. The development of such processes is strictly dependent on the ability to generate materials with high yield efficiency and production rate. We report a versatile and highly efficient method for synthesis of metal–organic frameworks in large quantities using continuous flow processing under microwave irradiation. Benchmark materials such as UiO‐66, MIL‐53(Al), and HKUST‐1 were obtained with remarkable mass, space–time yields, and often using stoichiometric amounts of reactants. In the case of UiO‐66 and MIL‐53(Al), we attained unprecedented space–time yields far greater than those reported previously. All of the syntheses were successfully extended to multi‐gram high quality products in a matter of minutes, proving the effectiveness of continuous flow microwave technology for the large scale production of metal–organic frameworks.     

Biocompatibility of nitrogen-doped multiwalled carbon nanotubes with murine fibroblasts and human hematopoietic stem cells

Journal of Nanoparticle Research - Workers are increasingly exposed to nanoparticles, mostly via inhalation. Respiratory protection is recommended as an additional control measure. Particulate...