A novel carbon/chitosan paste electrode for electrochemical detection of normetanephrine in the urine

Normetanephrine is a marker for pheochromocytoma, a rare catecholamine-secreting and neuroendocrine tumor, that arises from sympathetic and parasympathetic paraganglia. In this work, a novel carbon/chitosan electrode paste was used for sensitive voltammetric determination of normetanephrine and dopamine in the presence of ascorbic acid and uric acid. The modified electrode has shown an increase in the effective area of up to 68%, well-separated oxidation peaks, and an excellent electrocatalytic activity. The electrochemical response characteristics were investigated by cyclic and differential pulse voltammetry. Interestingly, high sensitivity and selectivity in the linear range of normetanephrine, dopamine, ascorbic acid, and uric acid concentrations were observed. The present method was applied in the urine sample and satisfactory results were obtained showing that this electrode is very suitable in pharmaceutical and clinical preparations.     

Substituent effects in the transannular cyclizations of germacranes. Synthesis of 6-epi-costunolide and five natural steiractinolides

The occurrence and orientation of substituents in the 10-membered ring characteristic of germacranes is determinant in the stereochemical outcome of the acid-promoted transannular cyclization of these metabolites. An explanation of the synthesis of eudesmanolides and guaianolides produced by the Umbelliferae family of plants is advanced. The syntheses of the natural products 6-epi-costunolide and five steiractinolides are reported.     

Film thickness effects on calibrations of a narrowband thermochromic liquid crystal

Thermochromic liquid crystals (TLCs) have been widely employed by researchers in heat transfer and fluid flow communities as a reliable and non-intrusive temperature measurement tool due to their unique optical properties such as birefringence, optical activity, circular dichroism and selective reflection of colours in the visible spectrum as function of temperature. The use of narrowband TLCs are attractive for temperature and heat transfer measurements due to their higher precision in temperature measurements and due to the fact that narrowband TLCs are less affected by variations in illumination-viewing angles and illumination disturbances. Narrowband TLCs have been used with full intensity-matching methods to provide robust image processing for measurements of thermal parameters in transient heat transfer tests. Calibration of narrowband TLCs is necessary in order to obtain the intensity-temperature relationship of the TLCs. Film thickness is one of the factors which affects calibrations of TLCs. In this research, film thicknesses of 10, 20, 30, 40 and 50 μm were investigated on green intensity-based calibrations of R35C1W TLC during heating and cooling. Results showed an increase in magnitude of peak green intensity with increasing film thickness, with a percentage increase of nearly 18% when film thickness increased from 10 to 50 μm. Results also showed an inconsistent shift in temperature at which peak green intensity occurs, with a maximum shift of 0.40 °C, suggesting that film thickness effects may be insignificant for narrowband TLCs compared with wideband TLCs. A theoretical method for estimating the volume of TLC coating required to achieve a desired film thickness has also been described in this paper, based on the surface area and dry solids content of the TLC. The method is easily implemented and applicable for sprayable TLC coatings.     

Synthesis of potent and orally efficacious 11β-hydroxysteroid dehydrogenase type 1 inhibitor HSD-016

Cortisol and the glucocorticoid receptor (GR) signaling pathway has been linked to the development of diabetes and metabolic syndrome. In vivo, 11β-hydroxysteroid dehydrogenase type 1 (11β-HSD1) catalyzes the conversion of inactive cortisone to its active form, cortisol. Existing clinical data have supported 11β-HSD1 as a valid therapeutic target for type 2 diabetes. In our research program, (R)-1,1,1-trifluoro-2-(3-((R)-4-(4-fluoro-2-(trifluoromethyl)phenyl)-2-methylpiperazin-1-ylsulfonyl)phenyl)propan-2-ol (HSD-016) was discovered to be a potent, selective, and efficacious 11β-HSD1 inhibitor and advanced as a clinical candidate. Herein, a reliable and scalable synthesis of HSD-016 is described. Key transformations include an asymmetric synthesis of a chiral tertiary alcohol via Sharpless dihydroxylation, epoxide formation, and subsequent mild reduction. This route ensured multikilogram quantities of HSD-016 necessary for clinical studies.     

Phosphonium-mediated cyclization of N-(2-aminophenyl)thioureas: efficient synthesis of 2-aminobenzimidazoles

BOP efficiently promoted the phosphonium-mediated cyclization of thioureas, leading to a convenient synthesis of 2-aminobenzimidazoles. Compared to conventional methods, the reactions were complete at room temperature with times ranging from a few minutes to 1 h in near quantitative yields. This method is also applicable to the synthesis of more challenging structures such as 2-akylaminobenzimidazoles and 2-(N-acyl)-aminobenzimidazoles. The methodology described herein represents a mild and efficient route to a variety of 2-aminobenzimidazoles.     

Ketene dithioacetals in the aza-Diels-Alder reaction with N-arylimines: a versatile approach to tetrahydroquinolines, 2,3-dihydro-4-quinolones,and 4-quinolones

[reaction: see text] The first successful use of ketene dithioacetals as dienophiles in the aza-Diels-Alder reaction with N-arylimines is described. Among the ketene dithioacetals tested, 1,4-benzodithiafulvenes are most effective in assembling the tetrahydroquinoline core. Subsequent chemical manipulations provide a concise and divergent approach to the synthesis of 2,3-tetrahydroquinolines, 2,3-dihydro-4-quinolones, and 4-quinolones.     

Biodegradable Materials from Agro-Based By-Products

Summary: A new biodegradable thermoplastic material based on a wheat flour by-product has been developed. The influence of various additives (glycerol, silica) and fibers (flax, cotton, hemp) on the mechanical properties of the material has been investigated. The development of expanded materials is also presented.