Routes To trans-Chrysanthemic Acid,IV1 Synthesis from 4-Acetyl-2-Carene

4-Acetyl-2-carene obtained from 3-carene undergoes methylation, ozonolysis, and lead tetraacetate oxidation resulting in cis-dihydrochrysanthemolactone.     

Organocatalytic Conjugate Addition of Azide Ion to α,β‐Unsaturated Aldehydes

An efficient and simple amine‐catatalyzed azide conjugate addition to α,β‐unsaturated aldehydes has been developed. In the presence of a catalytic amount of tertiary amine with a 1:1 mixture of NaN₃ and 37% HCl in CH₂Cl₂, α,β‐unsaturated aldehydes provided β‐azido aldehydes, which could be transformed into 1,3‐amino alcohols.     

Sodium Hypochlorite Reactions. III. The Catalytic Nakagawa and Related Systems

Mainly through the extensive investigations of Nakagawa and coworkers, nickel peroxide has emerged as a powerful oxidant for organic compounds. For example, it has been used for the oxidation of alcohols to aldehydes or carboxylic acids,^2,3 allylic hydroxyl (selectively) to the carbonyl group,⁴ α-ketols to α-diketones,⁵ α-glycols, α-ketols, α-hydroxyl and α-keto acids to cleavage products,⁶ aldehydes to amides or nitriles in the presence of ammonia,⁷ phenols to quinones,^8,9 certain Schiff bases to benzoxazoles,¹⁰ amines to azo compounds or nitriles,^11,12 diarylamines to hydrazines,¹³ carbazoles to dimers and trimers,¹⁴ hydrazones to diazo compounds,^15,16 1-aminobenzotriazole to benzyne,¹⁷ N-substituted hydroxylamines to azoxy compounds,¹⁸ phenylacetonitrile to dimeric products,¹⁹ a thiouracil to a uracil derivative,²⁰ thiols to disulfides and sulfides to sulfones,²¹ N-substituted phenothiazines to sulfoxides and sulfones,²¹ haloforms to hexahaloethanes.²³     

Determination of antioxidant activity using oxidative damage to plasmid DNA — pursuit of solvent optimization

Oxidative stress plays a key role in the pathophysiology of many diseases. Hydroxyl radical is the oxidative species most commonly causing damage to cells. The aim of this work was to optimize the method for antioxidant activity determination on a model lipophilic geranylated flavanone, diplacone. This method uses protection of plasmid DNA from oxidation by a hydroxyl radical generated by the Fenton reaction involving oxidation of metal ions using H₂O₂ and ascorbate. The method was optimized for lipophilic compounds using several solvents and co-solvents. It was found that (2-hydroxypropyl)-β-cyclodextrin (0.1 mass % aq. sol.) is the best co-solvent for our model lipophilic compound to measure the antioxidant activity by the method presented. Other solvents, namely dimethyl sulfoxide, Cremophor EL® (0.1 mass % aq. sol.), ethanol, and methanol, were not suitable for the determination of the antioxidant activity by the method described. Tween 80 (0.1 mass % aq. sol.) and a mixture of 10 vol. % ethanol and 9 mass % bovine serum albumin (aq. sol.) significantly decreased the antioxidant activity of the model lipophilic compound and thus were not suitable for this method.     

Interaction with the Surrounding Water Plays a Key Role in Determining the Aggregation Propensity of Proteins

Understanding the molecular determinants of the relative propensities of proteins to aggregate in a cellular environment is a central issue for treating protein‐aggregation diseases and developing peptide‐based therapeutics. Despite the expectation that protein aggregation can largely be attributed to direct protein–protein interactions, a crucial role the surrounding water in determining the aggregation propensity of proteins both in vitro and in vivo was identified. The overall protein hydrophobicity, defined solely by the hydration free energy of a protein in its monomeric state sampling its equilibrium structures, was shown to be the predominant determinant of protein aggregation propensity in aqueous solution. Striking discrimination of positively and negatively charged residues by the surrounding water was also found. This effect depends on the protein net charge and plays a crucial role in regulating the solubility of the protein. These results pave the way for the design of aggregation‐resistant proteins as biotherapeutics.     

Profiles of Essential Oils and Correlations with Phenolic Acids and Primary Metabolites in Flower Buds of Magnolia heptapeta and Magnolia denudata var. purpurascens

Magnolia flower buds are a source of herbal medicines with various active compounds. In this study, differences in the distribution and abundance of major essential oils, phenolic acids, and primary metabolites between white flower buds of Magnolia heptapeta and violet flower buds of Magnolia denudata var. purpurascens were characterised. A multivariate analysis revealed clear separation between the white and violet flower buds with respect to primary and secondary metabolites closely related to metabolic systems. White flower buds contained large amounts of monoterpene hydrocarbons (MH), phenolic acids, aromatic amino acids, and monosaccharides, related to the production of isoprenes, as MH precursors, and the activity of MH synthase. However, concentrations of β-myrcene, a major MH compound, were higher in violet flower buds than in white flower buds, possibly due to higher threonine levels and low acidic conditions induced by comparatively low levels of some organic acids. Moreover, levels of stress-related metabolites, such as oxygenated monoterpenes, proline, and glutamic acid, were higher in violet flower buds than in white flower buds. Our results support the feasibility of metabolic profiling for the identification of phytochemical differences and improve our understanding of the correlated biological pathways for primary and secondary metabolites.     

Event-triggered output-feedback tracking of a class of nonlinear systems with unknown time delays

A single function approximation (SFA) approach for event-triggered output-feedback tracker design is presented for uncertain nonlinear time-delay systems in lower-triangular form. Contrary to the existing event-triggered output-feedback control methods dependent on multiple function approximators in the presence of lower-triangular nonlinearities, the proposed SFA approach provides the following advantages: (i) the simple observer structure independent of function approximators; (ii) one event-triggering condition based on only a tracking error; and (iii) the simple control scheme using one function approximator. Thus, the structural simplicity is allowed for implementing the observer and the event-triggering law in the sensor part and the adaptive tracker in the control part. Under the proposed SFA-based event-triggered control scheme, it is shown that the boundedness of closed-loop signals and the existence of a minimum inter-event time are guaranteed regardless of unknown time-delay nonlinearities and unmeasurable state variables.