Unusually high enantioselectivity in high-performance liquid chromatography using cellulose tris(4-methylbenzoate) as a chiral stationary phase

The cellulose tris(4-methylbenzoate) chiral stationary phase (CSP) (commercially known as Chiralcel OJ-H) exhibited an extremely high enantioselectivity when used in the HPLC resolution of N-thiocarbamoyl-3-(4′-prenyloxy)-phenyl-5-phenyl-4,5-dihydro-(1H) pyrazole (Compound 1), in both normal-phase and polar organic conditions. Using n-hexane–ethanol (80:20, v/v) as a mobile phase, an enantioseparation factor value of 138.5 was found. In order to modulate the elution time of the longer retained enantiomer, a simple HPLC procedure was developed. The optimized analytical protocol was based on the stopped flow technique and did not involve any change in mobile phase composition. The stronger interaction energy of the (S) enantiomer compared to that of the (R) enantiomer was mainly attributed to the formation of a hydrogen bonding between the amino group of the thiocarbamoyl moiety and the carbonyl oxygen of the CSP.     

Interdonato lemon from Nizza di Sicilia (Italy): chemical composition of hexane extract of lemon peel and histochemical investigation

Considering that the determination of authenticity and of the geographical origin of food is a very challenging issue, in this study we studied by means of histological and histochemical analyses the famous Sicilian lemon known as ‘Interdonato Lemon of Messina PGI’. Since the protected geographical indication Interdonato lemon of Messina possesses high organoleptic properties, the composition of the hexane extract of lemon peel was determined by HRGC and HRGC–MS analyses and compared with that of lemon of different cultivars. The results obtained are informative of the oil’s quality and explain the variation of the lemon essential oil composition. Given the fundamental economic implications of any fraud, the aim of this study was to determine a fingerprint able to evaluate the authentication of the geographic origin in such way to prevent frauds in national and international markets.     

Trajectories Joining Two Submanifolds under the Action of Gravitational and Electromagnetic Fields on Static Spacetimes

In this paper we present existence and multiplicity results for orthogonal trajectories joining two submanifolds under the action of gravitational and electromagnetic fields on static spacetimes. These trajectories are critical points of unbounded functionals and they can be found by using a variant of the saddle point theorem and the relative category theory.     

Asymmetric synthesis of an N-acylpyrrolidine for inhibition of HCV polymerase

A practical asymmetric synthesis of a highly substituted N-acylpyrrolidine on multi-kilogram scale is described. The key step in the construction of the three stereocenters is a [3+2] cycloaddition of methyl acrylate and an imino ester prepared from l-leucine t-butyl ester hydrochloride and 2-thiazolecarboxaldehyde. The cycloaddition features novel asymmetric catalysis via a complex of silver acetate and a cinchona alkaloid, particularly hydroquinine, with complete diastereomeric control and up to 87% enantiomeric control. The alkaloid serves as a ligand as well as a base for the formation of the azomethine ylide or 1,3-dipole. Experiments have shown that the hydroxyl group of hydroquinine is a critical element for the enantioselectivities observed. The cycloaddition methodology is also applicable to methylvinyl ketone, providing access to either alpha- or beta-epimers of 4-acetylpyrrolidine depending on the reaction conditions utilized. The synthesis also highlights an efficient N-acylation, selective O- versus N-methylation, and a unique ester reduction with NaBH4-MeOH catalyzed by NaB(OAc)3H that not only achieves excellent chemoselectivity but also avoids formation of the undesired but thermodynamically favored epimer. The highly functionalized target is synthesized in seven linear steps from l-leucine t-butyl ester hydrochloride with all three isolated intermediates being highly crystalline.     

Convex domains of Finsler and Riemannian manifolds

A detailed study of the notions of convexity for a hypersurface in a Finsler manifold is carried out. In particular, the infinitesimal and local notions of convexity are shown to be equivalent. Our approach differs from Bishop??s one in his classical result (Bishop, Indiana Univ Math J 24:169?C172, 1974) for the Riemannian case. Ours not only can be extended to the Finsler setting but it also reduces the typical requirements of differentiability for the metric and it yields consequences on the multiplicity of connecting geodesics in the convex domain defined by the hypersurface.     

Selection of Anti‐gluten DNA Aptamers in a Deep Eutectic Solvent

Herein, we show the feasibility of using deep eutectic solvents as a faster way of selecting aptamers targeting poorly water‐soluble species. This unexplored concept is illustrated for gluten proteins. In this way, aptamer‐based gluten detection can be performed directly in the extraction media with improved detectability. We envision deep implications for applications not only in food safety control but also in biomedicine.     

MOF-Stabilized Perfluorinated Palladium Cages Catalyze the Additive-Free Aerobic Oxidation of Aliphatic Alcohols to Acids

Extremely high electrophilic metal complexes, composed by a metal cation and very electron poor σ-donor ancillary ligands, are expected to be privileged catalysts for oxidation reactions in organic chemistry. However, their low lifetime prevents any use in catalysis. Here we show the synthesis of fluorinated pyridine-Pd²⁺ coordinate cages within the channels of an anionic tridimensional metal-organic framework (MOF), and their use as efficient metal catalysts for the aerobic oxidation of aliphatic alcohols to carboxylic acids without any additive. Mechanistic studies strongly support that the MOF-stabilized coordination cage with perfluorinated ligands unleashes the full electrophilic potential of Pd²⁺ to dehydrogenate primary alcohols, without any base, and also to activate O₂ for the radical oxidation to the aldehyde intermediate. This study opens the door to design catalytic perfluorinated complexes for challenging organic transformations, where an extremely high electrophilic metal site is required.     

Combined Antimicrobial Effect of Bio-Waste Olive Leaf Extract and Remote Cold Atmospheric Plasma Effluent

A novel strategy involving Olive Leaf Extract (OLE) and Cold Atmospheric Plasma (CAP) was developed as a green antimicrobial treatment. Specifically, we reported a preliminary investigation on the combined use of OLE + CAP against three pathogens, chosen to represent medical and food industries (i.e., E. coli, S. aureus and L. innocua). The results indicated that a concentration of 100 mg/mL (total polyphenols) in OLE can exert an antimicrobial activity, but still insufficient for a total bacterial inactivation. By using plain OLE, we significantly reduced the growth of Gram positive S. aureus and L. innocua, but not Gram-negative E. coli. Instead, we demonstrated a remarkable decontamination effect of OLE + CAP in E. coli, S. aureus and L. innocua samples after 6 h. This effect was optimally maintained up to 24 h in S. aureus strain. E. coli and L. innocua grew again in 24 h. In the latter strain, OLE alone was most effective to significantly reduce bacterial growth. By further adjusting the parameters of OLE + CAP technology, e.g., OLE amount and CAP exposure, it could be possible to prolong the initial powerful decontamination over a longer time. Since OLE derives from a bio-waste and CAP is a non-thermal technology based on ionized air, we propose OLE + CAP as a potential green platform for bacterial decontamination. As a combination, OLE and CAP can lead to better antimicrobial activity than individually and may replace or complement conventional thermal procedures in food and biomedical industries.     

A New Photoactivatable Ruthenium(II) Complex with an Asymmetric Bis-Thiocarbohydrazone: Chemical and Biological Investigations

The synthesis, photoactivation and biological activity of a new piano-stool Ru(II) complex is herein reported. The peculiarity of this complex is that its monodentate ligand which undergoes the photodissociation is an asymmetric bis-thiocarbohydrazone ligand that possesses a pyridine moiety binding to Ru(II) and the other moiety contains a quinoline that endows the ligand with the capacity of chelating other metal ions. In this way, upon dissociation, the ligand can be released in the form of a metal complex. In this article, the double ability of this new Ru(II) complex to photorelease the ligand and to chelate copper and nickel is explored and confirmed. The biological activity of this compound is studied in cell line A549 revealing that, after irradiation, proliferation inhibition is reached at very low half maximal inhibitory concentration (IC₅₀) values. Further, biological assays reveal that the dinuclear complex containing Ni is internalized in cells.     

Electropolymerizable IrIII Complexes with β‐Ketoiminate Ancillary Ligands

A series of electropolymerizable cyclometallated Ir^III complexes were synthesized and their electrochemical and photophysical properties studied. The triphenylamine electropolymerizable fragment was introduced by using triphenylamine‐2‐phenylpyridine and, respectively, triphenylamine‐benzothiazole as cyclometalated ligands. The coordination sphere was completed by two differently substituted β‐ketoiminate ligands deriving from the condensation of acetylacetone or hexafluoroacetylacetone with para‐bromoaniline. The influence of the ‐CH₃/‐CF₃ substitution to the electrochemical and photophysical properties was investigated. Both complexes with CH₃ substituted β‐ketoiminate were emissive in solution and in solid state. Highly stable films were electrodeposited onto ITO coated glass substrates. Their emission was quenched by electron trapping within the polymeric network as proven by electrochemical studies. The ‐CF₃ substitution of the β‐ketoiminate leads instead to the quenching of the emission and inhibits electropolymerization.